JP3045565B2 - Film with excellent transparency and slip properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film having excellent transparency and slip properties, and more specifically, vinyl chloride widely used in agriculture, book covers, periodical use, and various other fields. The present invention relates to a film having transparency and slip properties without impairing the transparency of a resin film.

[0002]

2. Description of the Related Art A vinyl chloride resin film has excellent transparency, high mechanical strength, and is inexpensive.
Conventionally, it is widely used in the above-mentioned fields for agriculture, for book covers, for regular periods, for entering licenses for passports and vehicles, and in various other fields. However, vinyl chloride resin films are inferior in slipperiness, so they tend to stick to each other, and in agricultural films, it makes it difficult to work on the construction of houses and the opening and closing of the hem for ventilation inside the houses. In addition, in the case of a film for a book cover or a regular use, when the book or the regular use is taken in and out, the film adheres to the book or the regular use, and it is difficult to smoothly take in and take out the book.

Therefore, conventionally, at the time of forming a vinyl chloride resin film, an inorganic filler such as talc or silica is mixed with the resin, powder is formed at the time of forming, or the above-mentioned inorganic material is formed on the film surface after forming the film. A coating material containing a filler was applied, and the film was provided with irregularities due to the inorganic filler, and the irregularities ensured slip properties. That is, when a film is formed from a vinyl chloride resin blended with the above inorganic filler, when the base resin is stretched into a film by stretching at the time of molding, the dispersed particles appear on the surface or Irregularities are given to the film surface by being distributed in the vicinity. In the case of powdering treatment, the surface of the film is made uneven by the inorganic particles attached to the surface of the film. When the paint containing the above-mentioned inorganic filler is applied to the surface of the vinyl chloride resin film, the inorganic filler particles dispersed in the vicinity of the surface immediately after the application and the thickness of the film formed by the vehicle after the application and drying are obtained. Inorganic filler particles having the above particle size,
The surface of the film is provided with irregularities.

[0004]

However, the above-mentioned inorganic filler is different from the refractive index of the vinyl chloride resin film, and the cross-sectional shape of the filler is polygonal. This may hinder the transparency of the vinyl chloride resin film. Therefore, in order to increase the slip property of the vinyl chloride resin film, the amount of the inorganic filler used could not be increased. When the inorganic filler has a shape close to a sphere and has a small particle size, the transparency can be prevented to some extent, but the slip property cannot be improved. Although the slip property can be improved, the inhibition of transparency cannot be eliminated.

[0005] In the above-mentioned technique of forming and stretching a vinyl chloride resin blended with an inorganic filler into a film, the filler and the resin lack adhesiveness, so that when the resin is stretched into a thin film by stretching, As a result, the filler may be peeled off from the film, and fine voids may be generated at the peeled portion.
Since light is diffusely reflected in these minute gaps, if the gaps are formed innumerably throughout the film, the transparency of the film is greatly impaired. Such a phenomenon may occur similarly when the film is stretched even in the technique of applying the above-mentioned coating material containing the inorganic filler to the film surface.

The present invention solves all of the problems existing in the above-mentioned conventional technology for imparting slip properties to a vinyl chloride resin film, and maintains the excellent transparency of the vinyl chloride resin film, It is an object of the present invention to provide a technique for imparting a high degree of slip property.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted various studies in order to solve the above-mentioned object. As a result, the acrylic resin particles have a compatibility with the vinyl chloride resin and have a spherical shape. Since the refractive index is the same as or close to that of the vinyl chloride resin, it has been found that the acrylic resin particles may be used instead of the inorganic filler. The present invention is based on this finding. (1) Acrylic resin particles are kneaded into a vinyl chloride resin film, and the presence of the particles causes the film surface to have irregularities.
There excellent characteristics and transparency and slip properties to become formed film (hereinafter referred to as the first invention), (2) to at least one side acrylic resin particle layer of the vinyl chloride resin film is laminated And a film excellent in transparency and slip properties (hereinafter, referred to as a second invention).

The vinyl chloride resin in the first and second inventions includes polyvinyl chloride, a copolymer of another monomer copolymerizable with a vinyl chloride monomer, or a blend of these resins. Conventionally used resins can be used. Other monomers copolymerizable with the vinyl chloride monomer include, for example, ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid, acrylate, methacrylic acid, methacrylic ester, maleic acid, fumaric acid, acrylonitrile, and the like. Is mentioned.

Further, the acrylic resin particles in the first and second inventions include a homopolymer of an acrylic monomer,
Copolymers of acrylic monomers, copolymers of acrylic monomers and vinyl chloride monomers, acrylic rubber,
Acrylonitrile-based polymers, those which withstand high temperatures during kneading and are cross-linked to improve solvent resistance during coating, and acrylic polymers having a three-dimensionally cross-linked three-dimensional structure, etc. Since the refractive index is the same as or close to the refractive index of the vinyl chloride resin, it can be preferably used. These may be used alone or as a mixture of two or more. The shape of the acrylic resin particles is preferably spherical in order to reduce irregular reflection of light such as the above-mentioned inorganic filler.

Hereinafter, the average particle size and the mixing ratio of the acrylic resin particles will be described separately for the first invention and the second invention. In the first invention, the average particle size of the acrylic resin particles can be made larger than that of the above-mentioned inorganic filler. However, if it is too large, the original transparency of the above-mentioned vinyl chloride resin film is impaired, and it is too small. And about 1 to 10 [mu] m is preferable because the film does not exhibit an effective slip property imparting effect on the film. The mixing ratio of the acrylic resin particles to the vinyl chloride resin in the first invention can be larger than that in the case of the above-mentioned inorganic filler. Since the effect of imparting an effective slip property to the film is not exhibited even if the amount is too small, 0.1 to 3 parts by weight per 100 parts by weight of the vinyl chloride resin is used.
It is preferably 0 parts by weight. The film of the first invention comprises a resin composition obtained by mixing a plasticizer, a stabilizer, and other additives in addition to the above-mentioned vinyl chloride-based resin and acrylic resin particles in the same manner as a conventional film of this type. It is manufactured by molding and stretching.

The film of the second invention is obtained by laminating an acrylic resin particle layer on at least one surface of a vinyl chloride resin film, and the particle layer is made of the above-mentioned acrylic filler similarly to the case of the above-mentioned inorganic filler. The paint prepared by blending the resin particles in a vehicle is coated on both sides of a vinyl chloride resin film by rotary screen printing, reverse roll coating, doctor knife coating, gravure roll, spraying, rod coating, etc. It is laminated by applying it to one side. Therefore, this acrylic resin particle layer is a state in which the synthetic resin as a vehicle forms a thin coating film on the vinyl chloride resin film, and the acrylic resin particles are dispersed in the coating film.

The average particle size of the acrylic resin particles blended in the particle layer ranges from a large one having a particle size of about 30 μm to a very small one having a particle size of not more than 100 nm as compared with the case of the first invention. Can be used. That is, in the second invention, it is only necessary to uniformly disperse the acrylic resin particles in a resin (vehicle) serving as a base of the particle layer and coat the film on the film. Since it is not necessary to apply a process of uniformly kneading the resin into a resin and stretching and forming it into a film to obtain a predetermined thickness, it is effective to reduce the thickness of the coating film even if the particle size is extremely small. This is because slip properties are imparted.

Further, the mixing ratio of the acrylic resin particles is as follows:
Larger amounts can be used than with inorganic fillers, and smaller particle sizes can be used in larger amounts. However, when the particle size is relatively large, if the particle size is too large, the inherent transparency of the vinyl chloride resin film is impaired, and when the particle size is extremely small, if the particle size is too small, an effective slip property is imparted to the film. No effect is exhibited. Therefore, in the second invention, when the average particle size is relatively large, ie, about 30 to 0.5 μm, the base resin (vehicle) 100 of the layer has a solid content ratio.
It is preferably 0.1 to 30 parts by weight with respect to parts by weight, and when the average particle size is as small as about 100 nm or less, it is also preferably 0.1 to 50 parts by weight,
Also, in the case of an intermediate particle size between these two particle sizes, it is preferable that the content is also 0.1 to 30 parts by weight. It should be noted that these particles having various particle diameters may be mixed and used, and the mixing ratio of each particle size at this time may be appropriately selected within the range of the mixing ratio described above.

As the base resin (vehicle) of the acrylic resin particle layer, the resin used in the acrylic resin particles is used in consideration of the affinity with the acrylic resin particles and the adhesion to the vinyl chloride resin film. And the like, or compatible resins such as acrylic resin, urethane resin, cellulose resin, polyester resin, vinyl chloride resin and the like are used alone or as a blend. Particularly, an acrylic resin alone or a mixture of an acrylic resin and a vinyl chloride resin is preferable. If the base resin layer portion of the acrylic resin particle layer is too thin, the performance of the vehicle resin, such as antifouling properties, weather resistance, and the ability to prevent the transfer of additives, will be reduced. If it is too thick, the flexibility and bendability will be reduced. In the second aspect, the thickness is preferably about 0.5 to 5 μm because it leads to an increase in cost. In addition, the coating material as a raw material for laminating the acrylic resin particle layer includes, in addition to the base resin (vehicle), a plasticizer for softening a coating film, an ultraviolet absorber for improving weather resistance, a light stabilizer, A surfactant, a cross-linking agent, and other additives may be blended, and are prepared by adding an appropriate solvent thereto.

Further, the vinyl chloride resin film on which the particle layer is laminated is preferably a film obtained by molding and stretching a resin compound obtained by removing acrylic resin particles from the raw material for producing the film of the first invention. Can be used.

[0016]

According to the first aspect of the present invention, acrylic resin particles kneaded into a vinyl chloride resin film, particularly particles near the film surface, protrude from the film surface by stretching the film, and The surface is made uneven. Due to the unevenness, the film of the first invention secures a good slip property. At this time, since the acrylic resin particles have an affinity for the vinyl chloride resin, when the resin composition is molded and stretched to produce the film of the first invention, the base material of the film, such as the above-mentioned inorganic filler, is used. Is not separated from the vinyl chloride resin. Therefore, no fine voids are generated due to the peeling, and the inherent transparency of the vinyl chloride resin film is not reduced by the fine voids.

Further, since the refractive index of the acrylic resin particles is the same as or close to that of the vinyl chloride resin, even if kneaded in a large amount, the inherent transparency of the vinyl chloride resin film is not impaired. Furthermore, if spherical acrylic resin particles are used, irregular reflection of light by the particles does not occur, so even if a particle having a large particle size is used, the original transparency of the vinyl chloride resin film is not reduced. . Due to the characteristics (compatibility, refractive index, etc.) of the acrylic resin particles as described above, the average particle diameter of the vinyl chloride resin forming the base of the film of the first invention can be reduced without impairing the inherent transparency of the resin. Since a large amount of large acrylic resin particles can be kneaded in, the film of the first invention has good slip properties.

Further, in the film of the second invention, the acrylic resin particle layer laminated on at least one surface of the vinyl chloride resin film is formed by forming particles or particles near the surface of a thin film (coating film) composed of a base resin of the layer. Particles having a particle size larger than the thickness of the dried vehicle coating protrude from the surface of the coating,
The surface of the film is provided with irregularities. The film of the second invention secures a good slip property due to the unevenness of the film surface. And also in the film of the second invention, since the acrylic resin particles have adhesion to the base resin of the above-mentioned film, they do not peel off from the base resin even if secondary processing such as stretching is performed. Therefore, fine voids are not generated due to the peeling, and the fine voids do not lower the transparency of the vinyl chloride resin film. Also in the second invention, a large amount of acrylic resin particles can be compounded in the particle layer because of the refractive index of the acrylic resin particles,
If spherical acrylic resin particles are used, those having a large particle size can be used.

Further, in the case of very fine acrylic resin particles having an average particle size of nm class, even after forming the acrylic resin particle layer, the vinyl chloride resin film before forming the particle layer can be used. It shows almost the same transparency, and the transparency can be further improved as compared with the case where a large particle size is used. However, in the case of very fine acrylic resin particles of nm class, although the imparting property of the irregularities is slightly inferior, even if these fine particles are used in a large amount, they may hinder the transparency of the vinyl chloride resin film. The particles do not precipitate after being dispersed in the base resin (vehicle), and even if they do not precipitate, they are used in large quantities, so that the use of a large amount can ensure the imparting of unevenness and secure the slip property.

Due to the above-mentioned properties of the acrylic resin particles, the acrylic resin particles having a large average particle size and the nm-size particles can be used in the film of the second invention without impairing the inherent transparency of the vinyl chloride resin. Since the acrylic resin particle layer containing a large amount of fine acrylic resin particles can be laminated on the vinyl chloride resin film, the film of the second invention has good slip properties.

It is to be noted that the film of the first and second aspects of the present invention can be obtained by introducing an acidic group, a basic group, and a polar group into the acrylic resin particles in advance and making the surface of the particles themselves hydrophilic. It has excellent drip-proof properties. Moreover, the drip-proof property of the acrylic resin particles is maintained in a good state for a long period of time because the particles do not flow out due to dew condensation or the like.

[0022]

EXAMPLES Examples 1 to 3 The acrylic resin particles shown in Table 4 were added to the basic composition shown in Table 1 and a thickness of 0.1 was obtained using a calendar under the conditions shown in Table 2.
mm, and stretched into a film with a width of 200 cm.
An inventive film was obtained. The transparency and slip property of the obtained film of the first invention were evaluated using the evaluation items and evaluation criteria shown in Table 3, and the results are shown in Table 4. For reference, the presence or absence of microvoids was examined by using a 2000 × electron microscope photograph, and the results are also shown in Table 4.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

Comparative Example 1 A comparative film was prepared in the same manner as in Examples 1 to 3, except that talc shown in Table 4 was used in place of the acrylic resin particles. Evaluation was performed, and the results are also shown in Table 4.

[0027]

[Table 4]

Examples 4 to 7 A resin composition having the composition shown in Table 5 was molded and stretched under the same conditions as in Examples 1 to 3 into a film having a thickness of 0.3 mm and a width of 200 cm. A paint obtained by adding the acrylic resin particles shown in Table 8 to a paint having the basic formulation shown in Table 6
The coating was applied by a gravure coater to a dry thickness of 1.5 μm, dried at 130 ° C. for 30 seconds, and an acrylic resin particle layer was laminated to obtain a film of the second invention.
The transparency and slip property of the obtained film of the second invention were evaluated using the evaluation items and evaluation criteria shown in Table 7, and the results are shown in Table 8.

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

[0032]

[Table 8]

Example 8 A resin composition having the composition shown in Table 9 was molded and stretched under the same conditions as in Examples 1 to 3 into a film having a thickness of 0.1 mm and a width of 200 cm. The paint 1 having the composition shown in FIG. 10 and the paint 2 having the composition shown in Table 11 on the other side were each subjected to rod coating to obtain a coating 1 and a paint 2 having a dry thickness of 0.1.
The film was applied so as to have a thickness of 5,0.6 μm, dried at 85 ° C. for 30 seconds, and an acrylic resin particle layer was laminated thereon to obtain a film of the second invention. The transparency and slip property of this film were evaluated based on the evaluation items and evaluation criteria shown in Table 3 of Examples 1 to 3, and the drip-proof property (drip-proof durability) was spread so that the paint 1 was on the inside. Are evaluated according to the evaluation items and evaluation criteria shown in Table 2, and the results are shown in Table 14.

[0034]

[Table 9]

[0035]

[Table 10]

[0036]

[Table 11]

[0037]

[Table 12]

Example 9 One side of the film prepared in Example 8 was applied to Table 1 of Example 8
In the same manner as in Example 8, a paint 2 having a composition shown in Table 1 was applied so as to have a dry thickness of 0.6 and 1.3 μm, respectively. Example 8
Dry in the same manner as above to laminate the acrylic resin particle layer,
An inventive film was obtained. The transparency, slip property and drip-proof property (drip-proof durability) of the obtained film of the second invention were evaluated by spreading the paint 2 on the inner surface and evaluating it in the same manner as in Example 8. 14 together.

[0039]

[Table 13]

[0040]

[Table 14]

Example 10 A resin composition having the composition shown in Table 15 was molded and stretched into a film having a thickness of 0.2 mm and a width of 200 cm under the same conditions as in Examples 1 to 3, and applied to one surface of the film. Paint 1 shown in Table 10 of Example 8 and Paint 2 shown in Table 11 of Example 8 on the other side were the same as in Example 8, and the dry thickness of paints 1 and 2 was 0.1.
It was applied so as to have a thickness of 5, 0.6 μm, dried in the same manner as in Example 8, and an acrylic resin particle layer was laminated thereon to obtain a film of the second invention. As a result of evaluating the transparency and the slip property of this film by the evaluation items and evaluation criteria shown in Table 7 of Examples 4 to 7, all were ○.

[0042]

[Table 15]

[0043]

As described above in detail, according to the first and second aspects of the present invention, as a material for imparting unevenness to a vinyl chloride resin film, it has an affinity for the vinyl chloride resin, and Acrylic resin particles having a similar refractive index and capable of preparing a spherical one are used, so that the film has good slip properties without impairing the original transparency of the vinyl chloride resin film. Can be granted. As a result, according to the films of the first and second inventions, the situation in which the films adhere to each other is eliminated, and when the films of the first and second inventions are used as agricultural films, construction work such as a house or a house The opening and closing work of the hem for ventilation of the inside can be facilitated, and when it is used as a general-purpose film for book covers, regular use, etc., it is possible to obtain an effect of smoothly putting in and taking out books and regular use. In addition, acrylic resin particles have weather resistance,
Because it is also excellent in light resistance, stain resistance, dust resistance, etc.
The film of the second invention also has these excellent properties, and is extremely effective as the above-mentioned agricultural film or general film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI B32B 27/30 101 B29C 67/16 // B29K 27:06 105: 16 B29L 7:00 9:00 C08L 27:06

Claims (2)

(57) [Claims] 1. Acrylic resin particles are kneaded into a vinyl chloride resin film, and the presence of the particles causes the film surface to be kneaded.
A film having excellent transparency and slip properties, characterized by having irregularities formed on the surface . 2. A film having excellent transparency and slip properties, wherein an acrylic resin particle layer is laminated on at least one surface of a vinyl chloride resin film.