JPS58224745A - Bag-shaped container for storing office supplies - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bag-like container for storing office supplies. In detail, 1. There is little transfer of printing ink from printed matter printed with various inks, there is little contamination by printing ink, etc., and even if the printed matter is stored and stored for a long time,
The present invention relates to a bag-shaped container for storing office supplies made of a vinyl chloride resin film that does not cause printing ink to fade or discolor.

Vinyl chloride resin depends on the type of plasticizer added to it,
By varying the blending amount, etc., the flexibility (hardness) of the molded product obtained from the blended composition can be adjusted, and excellent physical properties can be exhibited depending on the application, so it is widely used. The field is extremely wide-ranging.

One of the application fields is for packaging various printed matter.

Printed matter is printed using conventional printing techniques such as letterpress printing, intaglio printing, planographic printing, and stencil printing, as well as electrostatic copying.

Some copies are made using copying techniques such as thermal copying and pressure-sensitive copying. There are a wide variety of inks used for these printed materials and copies.The various printed materials produced using the above-mentioned printability and copying methods are organized into various files for convenient storage, organization, and removal. It is often stored in a storage bag.

In addition to paper, the material used for storage bags is made from transparent synthetic resin film. Polyethylene, polyethylene, and vinyl chloride resins are used as transparent synthetic resin film materials.

Soft vinyl chloride thread resin is most commonly used because it has excellent adhesive workability and processability.

However, films made of soft vinyl chloride resin
The ml plasticizer and other additives mixed therein migrate to the film surface and ooze out over time. For this reason, if printed matter is stored in a flat bag-like container made from this film for a long period of time, the inner surface of the container and the printed surface will adhere to each other, and if they are forcibly peeled off, the ink may be transferred to the inner surface of the container and cause contamination. In some cases, problems have arisen in which the printing ink fades or the printed characters completely disappear.

Techniques to solve these problems include laminating a soft vinyl chloride resin film as a base and a film made of another resin to form a laminated film, and forming a film by applying another resin. A technique has been proposed.

Among the improved technologies mentioned above, the technologies used for laminated films are: tightness between the base vinyl chloride resin film and films made of other resins, adhesive strength, transparency of the laminated film, texture, and adhesion by high-frequency welding. For these reasons, it is difficult to select a resin film for 1aNI.

Among the above-mentioned improved techniques, the technique of coating other resins to form a coating has a problem in that the coating becomes white when the hole is bent when documents are put in or taken out of the storage container.

As a result of intensive study to provide a container for storing office supplies that eliminates the technical problems described above, the inventors of the present invention have developed a method by treating the surface of a soft vinyl chloride resin film containing a specific plasticizer with low-temperature plasma. The present inventors have discovered that the problem can be solved by forming a bag-like container by forming a specific crosslinked layer, overlapping the crosslinked layers, and sliding them at desired locations, and have completed the present invention.

Therefore, the gist of the present invention is that 100 parts by weight of a vinyl chloride resin contains 20 to 80 parts by weight of a plasticizer containing at least 10 parts by weight of a plasticizer having an aromatic ring in the molecule.
parts by weight of the resin composition is formed into a film, and on at least one side of the film.

In a bag-like container for storing office supplies, a cross-linked layer 1- is formed by subjecting it to low-temperature plasma treatment using a gas that does not have plasma properties, and the cross-linked layers are overlapped and bonded at desired points. The thickness is 0.Ol to 1 micron,
The weight of the insoluble matter in tetrahydrofuran is 9'NJ or more, the degree of chlorination is less than 45 times the degree of chlorination of the non-crosslinked layer, and the light transmittance at a wavelength of 555 mIJi Gron of the film with the crosslinked layer is low temperature plasma treatment. A bag-like container for storing office supplies, characterized in that the light transmittance of the original film is 80qIb or more.

The present invention will be explained in detail below.

In the present invention, the vinyl chloride thread resin means polyvinyl chloride and a copolymer mainly composed of vinyl chloride. Monomers that copolymerize with vinyl chloride include vinyl esters, vinyl ethers, acrylic acid or methacrylic acid and their esters, maleic acid or fumaric acid and their esters, maleic anhydride, aromatic vinyl compounds, Examples include vinylidene compounds, acrylonitrile, metaglylonitrile, ethylene, and propylene.

The vinyl chloride resin contains a plasticizer containing at least 10 plasticizers having an aromatic ring in one molecule,
20 to 80 parts by weight per 100 parts by weight of resin.

The reason why it is essential to use a type of plasticizer that has an aromatic ring in one molecule is that the film containing this Tsubomachi plasticizer has a surface number W (crosslinked) by low-temperature plasma treatment. This is because the effect is noticeable.

Examples of plasticizers having an aromatic ring in the molecule include dibutyl phthalate, diethyl phthalate, dibutyl phthalate, dibutyl phthalate, diheptyl phthalate, and di-2-ethylhexyl phthalate.

Diisoogtyl phthalate, di-n-octyl phthalate,
Dinonyl phthalate, isodecyl phthalate.

Ditridecyl phthalate, dicyglohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, phthalic acid mixed ester (Ov ~ 0. Phthalate esters of hemorrhoids) Trimeridic acid esters such as trimethyl trimellidate, trioctyl trimellidate, etc. Plasticizers such as ethyl phthalyl ethyl glyflate, butyl phthalyl butyl glycolate, diethylene glycol dibenzoate, and dibutyl tetrahydrophthalate are exemplified.

A type of plasticizer that does not have an aromatic ring in one molecule may be mixed with the above plasticizer. Examples of such plasticizers include aliphatic dibasic acid esters such as dibutyl adipate, diisodecyl adipate, dioctyl azelate, and dibutyl sepacate, butyl oleate, and methyl acetyl ricinoleate.

Chlorinated fatty acid methyl, methoxychlorinated fatty acid methyl, etc. (
D jl Fatty esters? Examples include acetyl tributyl citrate, chlorinated paraffin, polyp-a-pyrene adipate, poly-1a-pyrene-y sepagate, and the like.

Since it is difficult to form a crosslinked layer by low-temperature plasma treatment using only the latter type of plasticizer that does not have an aromatic ring in the molecule, use a type of plasticizer that does not have an aromatic ring in the molecule. In some cases, at least one of the IOs is required to contain a plasticizer having an aromatic ring in the molecule.

The blending amount of such a plasticizer in the vinyl chloride resin is 20 to 801 parts by weight per 100 parts by weight of the resin to facilitate the film-forming action, and when the surface of the film is subjected to low-temperature plasma treatment, the surface A preferable crosslinked layer is formed, and the film on which the crosslinked layer is formed is also suitable because it is easy to process later.

In the present invention, in addition to the plasticizers listed in MU, other resin additives 1 such as heat stabilizers and lubricants may be added to the above-mentioned flexible blended vinyl chloride resin composition.

Anti-fogging agents, antifogging agents, pigments, dyes, fillers, etc. can be added.

The vine stabilizers used include calcium stearate,
Jinpeng soaps such as zinc stearate, barium stearate, cadmium stearate, tribasic lead sulfate, dibasic lead phosphite, dibutyltin laurate, dibutyltin simalate, di-n-octyltin mercaptide,
Examples include organic tin compounds such as dimethylstin mercaptide.

The lubricants used include butyl stearate + 7) ester thread lubricants, fatty acid amides such as ethylene bisstearamide, and stearic acid.

Examples include higher fatty acids such as palmitic acid and t-styric acid, and polyethylene wax.

As a Vine Band 111 inhibitor or antifogging agent to be used.

Sorbitan thread surfactants such as sorbitan monostearate, sorbitan monopalmitate, sorbitan monobenzoate - Glycerin surfactants such as glycerin monolaurate, diglycerin monopalmitate, glycerin monostearate, polyethylene glycol monostearate, Polyethylene glycofur-based surfactants such as polyethylene glycofur monopalmitate? Examples include alkylene oxide adducts of alkylphenols, esters of resorbidan/glycerin condensates, and organic acids.

The amount of the resin additive in each of the above-mentioned buildings relative to the base vinyl chloride resin can be selected within a range of 5 parts by weight or less per 10.0 parts by weight of the resin.

To blend plasticizers and various resin additives into the base vinyl chloride resin, use conventional blending techniques, mixing techniques 1, such as ribbon blenders, Banbury mixers, super mixers, and other conventionally known blenders and mixers. It's fine to use.

To form a film from the resin composition obtained in this way, methods known per se may be employed, such as melt extrusion molding (inflation method, T-die method), solution casting method, and calender molding method. . The surface of the film may be smooth or may be embossed on one side. The thickness of the film can be selected from a range of 0.055w+1 to 4m+.

In the present invention, at least one side of the film obtained by the above method is subjected to low temperature plasma treatment to form a crosslinked layer. The method of low-temperature plasma treatment is under a pressure of 10) to 10) liters.

The surface of the white film may be treated with low-temperature plasma of a gas that does not have plasma polymerizability. The plasma generation conditions at this time are 1, for example, 13.56M between 11IL#jI
It is sufficient to apply a power of Hz, lO to 500W, and the plasma treatment time varies depending on the applied plasticity, but is generally in the range of several seconds to several tens of minutes. In addition to the methods described above, various methods can be used, such as high frequencies, low frequencies, microwaves, etc. in the discharge frequency band of several KHz to several hundred MHz. In addition to glow discharge, plasma generation methods also include
Spark discharge, silent discharge, etc. can also be employed. Also,
The electrodes may be external electrodes, internal chambers, poles, coil types, etc., and may be capacitively coupled or dielectrically coupled. However, whatever method is used, care must be taken to prevent the surface of the film from being altered by the discharge heat.

Gases that do not have plasma polymerizability are preferably inorganic or inert gases, such as helium, neon, argon, nitrogen, nitrous oxide, nitrogen dioxide, oxygen, air,
Examples include chlorine, hydrogen chloride, carbon oxide, carbon dioxide, and hydrogen. These gases can be used alone or
May be used in combination. plasma! The desired plasma can be generated satisfactorily by setting the pressure of these gases in the q-generation device to 10 to 10 torr.

As described above, when the surface of a vinyl chloride resin film is subjected to plasma treatment, a crosslinked layer is formed on the surface of the film.

This crosslinked layer has a thickness of 0.01 to 100 g.

The tetrahydrofuran insoluble content is 900 parts by weight or more, and the degree of chlorination is 45 parts or less than the degree of chlorination of the non-crosslinked layer.

The crosslinking m is 11! It can be measured using a microscope, and its thickness is preferably 0.01 to li microns. If the thickness is thinner than 0.01tgron.

Since the crosslinking density of the crosslinked layer is insufficient and the thickness of the crosslinked layer, which acts as a diffusion barrier for low molecular weight substances, is also insufficient, low molecular weight substances can be diffused and eluted. The eluted low-molecular substances come into contact with the printed matter stored in the container, adsorbing the printing ink, or fading the printing ink.

It is bleached. In addition, when the crosslinked layer is thicker than ljgron, the crosslinked density becomes high, and the crosslinked layer becomes hard and even slight mechanical deformation causes cracks in the crosslinked layer.
It may devitrify, or low-molecular substances may diffuse and elute through these cracks.
Similar problems arise when the crosslinked layer is thin.

The crosslinking density of the crosslinked layer is @V of the tetrahydrofuran-insoluble content.
It can be determined by C that the crosslinked layer is almost insoluble in tetrahtomifuran and only slightly swells. The crosslinking density is sufficient when the insoluble content in tetrahtomifuran is 90 mo or more.

The degree of chlorination of the crosslinked layer is 45 degrees or less of the degree of chlorination of the non-crosslinked layer. Crosslinking of vinyl chloride resin is thought to occur while dechlorination reaction is being carried out, and the lower the degree of chlorination of the crosslinked layer 1 □ bridge j− than the degree of chlorination of the non-crosslinked layer, the higher the crosslinking density. In the present invention, the degree of chlorination of the crosslinked layer is 45 or more than the degree of chlorination of the uncrosslinked layer.

This is not preferable because the degree of crosslinking is insufficient and it is not possible to prevent low molecular weight substances from diffusing in the crosslinked layer and eluting to the surface of the crosslinked layer.

What is the degree of chlorination of the crosslinked and non-crosslinked layers of the film?

It can be converted to T1 by organic chlorine elemental analysis, XP8 (X-ray optical spectroscopy) analysis, XMA (X-ray microanalysis) analysis, etc. The organic chlorine elemental analysis method consists of burning and decomposing the crosslinked layer and non-crosslinked layer resin in two flasks under a zero oxygen atmosphere, absorbing the generated chlorine in a colored water hydrazine solution, and then performing potentiometric titration with silver nitrate. Determine the chlorine content using the method.

This is a method to determine the degree of chlorination. In the xP8 analysis method.

) 15 The degree of chlorination can be determined from the ratio of the area of the ols peak to the area of the 011p peak (oztp 10HB ) of the crosslinked layer and non-crosslinked layer resin determined by a photoelectron spectrometer. In the XMA analysis method.

The degree of chlorination of the crosslinked layer and non-crosslinked layer can be directly determined using an X-ray microanalysis device.
1' has a light transmittance at a wavelength of 555 millimicrons that is 80 mm or more than the light transmittance (at a wavelength of 555 millimicrons) of the original film subjected to low-temperature plasma treatment. The light transmittance of a film with layers varies depending on the thickness of the crosslinked layer, crosslink density, chlorination rate, etc., but if it is lower than 80 degrees compared to the light transmittance of the original film before low-temperature plasma treatment, it will become transparent. This is undesirable as it reduces performance.

The bag-like container according to the present invention is a planar bag-like container in which crosslinked layers of films having the above-mentioned properties are stacked on top of each other and are slid at desired locations. The film can be cut to the desired size in advance, or it can be wound into a roll [
You can leave it there. To bond the desired location, there are methods using a high frequency welder, ultrasonic waves, heat,
Any method such as using an adhesive may be used.

The shape of the bag-like container according to the present invention can be square, long sword-shaped, triangular, circular, oval, or various other shapes in plan view.

The bag-shaped container according to the present invention has the following effects, and its industrial utility value is extremely large.

(υ Since the cross-linked layer is formed on the article storage side of the bag-like container according to the present invention, the diffusion and elution of the low-molecular-weight compound blended into the film to the surface is preferably suppressed, and the cross-linked layer and printed matter are Even if they come into contact.

Printing ink does not adhere or fade.

(2) On the article storage section side of the bag-like container according to the present invention.

Although a crosslinked layer with special photographic properties is formed.

Even if this layer is subjected to mechanical deformation, the crosslinked layer is less prone to cracking and devitrification is less likely to occur.

(3) The bag-like container according to the present invention can be easily manufactured using conventionally known techniques, even though a crosslinked layer is formed on at least one side of the film for manufacturing the bag-like container. 0 or Less 1 The present invention will be described in detail based on examples, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

Example 1 Comparative Example 1 (Preparation of film) Polychlorinated beer (P-1050) 100 parts by weight Diogtylphthalate 30 l Epoxidized soybean oil
31 barium-zinc liquid stabilizer
ll barium-zinc powder stabilizer 0.51
First, a resin composition consisting of the following is prepared. Next, this resin composition was fed to a calender roll heated to 165° C. and kneaded to form a film with a thickness of 0.1 m. This is called film 1.

(Plasma processing Set the film l in the plasma generator.

Under reduced pressure - while venting carbon oxide gas, the pressure is reduced to 0,4
) Adjusted and held at 7L/, 13.56MHz 100
One side of the film was bent for 3 minutes by applying a high frequency of W and causing a discharge to generate plasma.

This is called film 2.

For film 2, the thickness of the crosslinked layer, tetrahydrofuran insoluble content, and degree of chlorination were measured, and for film 1 and film 2, the wavelength was 1555! ! The light transmittance in Itchron was measured. The measurement results are shown in the taX table.

The details of the measurement method are as follows.

Measurement of the thickness of the crosslinked layer: The cut surface of the film was stained with 0s04, and then measured using an electron microscope.

Tetrahydrofuran-insoluble matter: scrape off the crosslinked layer from the film surface and disperse it in tetrahydrofuran! After standing for day and night, the insoluble matter was separated using a centrifuge, the separated material was dried, the weight was measured, and the weight ratio to the original sample was calculated.

Degree of chlorination: The crosslinked layer and non-crosslinked layer were determined by organic chlorine elemental analysis.

Light transmittance: Hitachi spectrophotometer model 323, wavelength 55
Transmission was measured at 5 millimicrons.

c) Preparation of a bag-like container) A bag-like container was prepared in the manner shown in FIG. 1 and Factor 2. That is, the above film l and film 2, l 2IM
Cut the film to a size of I As shown in FIG. 2, a large number of bag-shaped containers were made by sliding the container at a position 5- from the end as shown in FIG. 2 using a high-frequency welder.

In FIGS. 1 and 2, 1 is a non-crosslinked layer of the film;
2 is a crosslinked layer.

In addition, FIG. 3 is a partial cross-sectional view showing how a bag-like container made of a film whose both surfaces have been subjected to low-temperature plasma treatment is used. , 4Vi contents are shown respectively.

(Test for storing printed matter in a bag-like container) Printed matter copied using various copying methods was
The pieces were cut into pieces with dimensions of , and placed one by one into a bag-shaped container prepared by the above method. These bag-shaped containers were sandwiched between glass slopes, a load of 7 kg was placed on the top glass plate, and the containers were left at a temperature of 50°C for 24 hours.Then, the printed matter was removed from the containers, and the inside surface of the containers was The condition of the printed matter was visually observed.

The results are shown in Table 1.

Table 1 0: No ink transfer to the inner surface of the container.

○: Very slight transfer of ink to the inner surface of the container is observed.

△... Ink transfer to the inner surface of the container is observed in a thin manner over the entire surface, and some areas have dark transfer areas.

×: The transfer of ink to the inner surface of the container is visible all over the surface.

××: Ink transfer to the inside surface of the container is observed in a dark manner over the entire surface, as well as blocking between the film and the printed matter.

Table 1 shows that the bag-shaped container according to the present invention does not cause problems such as fading or discoloration of printing ink caused by various types of copying, and further shows that there is less transfer of printing ink and less contamination by printing ink. ing.

Example 2 Comparative Example 2 (Preparation of film) Polyvinyl chloride (P=1050) 100 parts by weight vi-glyphthalate 40 1 Epoxidized soybean oil
31 barium-zinc liquid stabilizer
if parikumu zinc powder stabilizer 0.51
A resin composition consisting of the following was prepared without hesitation. Next, this resin composition was fed to a calender roll heated to 165° C. and kneaded to form a film having a thickness of Q and 14 mm. This is called film 3.

(Plasma treatment) Set the Fill Cold 3 in the plasma generator and heat it under reduced pressure.
One side of the film was treated for 10 minutes by generating plasma by adjusting and maintaining the pressure at 0.2 torr while passing carbon oxide gas through it and applying and releasing a high frequency wave of 13.56 MHz and 50 W. One side of the film was treated for 10 minutes. This is called film 4.

For film 4, the thickness of the crosslinked layer and the tetrahydrofuran insoluble content were the same as for film 20s.

The degree of chlorination was measured, and the light transmittance at a wavelength s 55 i 1J micron was measured for Film 3 and Film 4.

The measurement results are shown in Table 2.

C) Creation of bag-shaped container) Example 1. It was prepared in the same manner as in Comparative Example 1.

C) Printed matter storage test in bag-shaped container) Example 1. The same procedure as in Comparative Example 1 was carried out.

The results are shown in Table 2.

Table 2 Note 2: The display of observation results is the same as in Table 1.

Table 2 shows that, as in Table 1, the bag-shaped container according to the present invention does not cause problems such as fading or discoloration of printing ink caused by various copying methods, and furthermore, This shows that there is little pollution.

[Brief explanation of drawings]

Figures 1 and 2 show the creation of a bag-like container in this example, and Figure 1 shows the state in which two films are overlapped. FIG. 2 shows the state of high-frequency bonding. FIG. 3 is a partial cross-sectional view showing how a bag-like container made of a film whose both sides are subjected to low-temperature plasma treatment is used. 1... Non-crosslinked layer of the film, 2, 3... Crosslinked layer. 4...Contents.

Claims (1)

[Scope of Claims] 1. A resin composition containing 20 to 80 parts by weight of a plasticizer containing at least 10 parts of a plasticizer having an aromatic ring in the molecule per 100 parts by weight of a vinyl chloride resin. is formed into a film, at least one side of this film is subjected to low-temperature plasma treatment with a gas that does not have plasma polymerizability to form a crosslinked layer, and the crosslinked layers are overlapped and bonded at desired points. In a shaped container. The thickness of the crosslinked layer is 0.0! The insoluble content of tetrahydrofuran is 90% by weight or more.The degree of chlorination is less than 45 times the degree of chlorination of the non-crosslinked layer, and the wavelength of the film with the crosslinked layer is 556 mg (light transmittance in A bag-shaped container for storing office supplies, characterized in that the light transmittance of the raw film of the low-temperature plasma treatment material is 8 (1 or more).