JPS5954015B2 - Manufacturing method of vinyl chloride resin film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a vinyl chloride resin film that is matte, non-sticky, and has an excellent texture.

Conventionally, vinyl chloride resin films used for diaper covers, book covers, etc. have been mixed with a large amount of filler or embossed in order to eliminate the gloss on the surface and to eliminate the stickiness that is unique to vinyl chloride resin films. Processing etc. have been carried out.

With these methods, for example, the strength of the film obtained is low with the former method, and with the latter method it is not possible to obtain a film with sufficient gloss, and furthermore, the stickiness peculiar to vinyl chloride resin films cannot be completely removed. The texture was extremely bad. In addition, for the purpose of obtaining matte molded products, a vinyl chloride resin composition with a matte effect was disclosed in Japanese Patent Application Laid-open No. 54-11.
Although it is known from Japanese Patent No. 7550, etc., the resin composition has a low tensile strength and is used exclusively for thick products such as injection molded products, extrusion molded products, and compression molded products, and is used for applications that require high-speed take-up. I never expected to use it for calendar processing.

The inventors of the present invention aimed to provide a vinyl chloride resin film that is matte, non-sticky, and has an extremely excellent texture. It has been found that the material added and plasticized can be calendered, and the resulting film is matte, non-sticky, and has an extremely excellent texture.

Furthermore, it was discovered that the film can maintain its matte state even if it is laminated with other molten resin, leading to the present invention. That is, the gist of the present invention is to combine 5 to 90 parts by weight of a crosslinked vinyl chloride polymer with a gel fraction of 60% or less, a swelling degree of 5 or more, and an average particle size of 70μ or less, and a non-crosslinked vinyl chloride polymer (hereinafter simply " (referred to as “vinyl chloride polymer”) 95
A method for producing a vinyl chloride resin film, which comprises blending and kneading 10 to 10 polymer parts and 20 to 200 plasticizers and then calendering at a temperature of 140 to 200C.

To explain the present invention in detail, the cross-linked vinyl chloride polymer used in the method of the present invention is a mixture of vinyl chloride monomer or a vinyl chloride monomer and a comonomer copolymerizable therewith, and has a plurality of active double bonds in the molecule. It is obtained by reacting a compound that has a bond and is copolymerizable with the monomer or comonomer.

A compound with multiple active double bonds in its molecule is
An active double bond exhibiting radical polymerization behavior between a vinyl chloride monomer or a comonomer copolymerizable with it,
Preferably, it has 2 to 3, and moreover, it is preferably one that can be easily copolymerized with vinyl chloride monomer or comonomer. Examples of such compounds include diallyl compounds, triallyl compounds, divinyl compounds, diacrylic or triacrylic compounds, and specific examples include diallyl phthalate, diallyl adipate, diallyl maleate, diallyl succinate, diallyl carbinol, Triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, divinylbenzene, divinyl ether, divinyl sulfone, 2,6-
diacrylphenol, glycerin triacrylate,
Examples include glycerin trimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and among these, diallyl phthalate and triallyl cyanurate are particularly preferred. These compounds act as crosslinking agents in the vinyl chloride polymer produced. Therefore, the compound used for the polymer (hereinafter referred to as "crosslinking agent").

) is not limited to one type, and it goes without saying that two or more types may be used. The proportion of vinyl chloride monomer and crosslinking agent to be used depends on the manufacturing conditions of the crosslinked polymer, but usually the latter is 0.001% by weight or more, preferably 0. .0
It is preferably used in a range of 0.01 to 1% by weight, and particularly preferably in a range of 0.05 to 0.5% by weight. When the amount of the crosslinking agent is less than 0.001% by weight, almost no crosslinking effect due to copolymerization is observed, while when it is more than 1% by weight, depending on the manufacturing conditions, a network structure is likely to occur. This often impedes melt flow and makes processing difficult. Of course, this does not preclude the use of a crosslinking agent of 1% by weight or more. It will also be described later as a vinyl chloride monomer. When a mixture of comonomers and a crosslinking agent are copolymerized, the amount of the crosslinking agent is preferably determined in consideration of the copolymerizability of the comonomer with the crosslinking agent. Examples of comonomers copolymerizable with vinyl chloride monomers that can be used in the production of crosslinked vinyl chloride polymers include olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, ethyl vinyl ether, Vinyl ethers such as cetyl vinyl ether, acrylic esters such as butyl acrylate, methyl methacrylate,
Anhydrides or esters of maleic acid and fumaric acid, nitrile compounds such as acrylonitrile, other styrene,
Examples include acrylic acid and methacrylic acid, and there are no particular limitations as long as they do not have a plurality of active double bonds in their molecules and can be copolymerized with vinyl chloride monomers.

Further, the amount of the comonomer used is preferably 30% by weight or less based on the total amount of the comonomer and the vinyl chloride monomer. The crosslinked vinyl chloride polymer is prepared by combining a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a comonomer copolymerizable therewith with a crosslinking agent such as diisopropylene peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, acetyl chloride, etc. Oil-soluble polymerization initiators such as organic peroxides such as cyclohexylsulfonyl peroxide, t-butylperoxypivalate, and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile. , partially saponified polyvinyl acetate, cellulose derivatives, etc., in the presence of suspending agents or emulsifying agents, and other auxiliary agents, by employing various methods such as suspension polymerization and emulsion polymerization.

By appropriately selecting the manufacturing conditions, crosslinked polymers having various average particle diameters, gel fractions, and degrees of swelling can be obtained. The crosslinked polymer used in the method of the present invention has these shapes,
Although not particularly limited to physical properties, it is preferable that the average particle size is 70μ or less in order to prevent roughening of the surface of the molded product. In consideration of good texture, average particle size 10-70μ, preferably 30-60μ, gel fraction 60%
Hereinafter, it is convenient to select from the range of preferably 3 to 60% and a swelling degree of 5 or more. Therefore, the gel fraction, degree of swelling, and average particle size are values measured as follows.

(1) Gel fraction: represents the degree of crosslinking.

Accurately weigh 2 grams (Gr) of cross-linked vinyl chloride polymer, put this into a 500 milliliter (ml) glass beaker together with 400 gr of tetrahydrofuran (THF), stir and dissolve at room temperature for 1 hour, and pour this into a 500 milliliter (ml) glass beaker. The undissolved content of the cross-linked vinyl chloride polymer is removed.

The weight Wlgr of the insoluble matter after drying is accurately weighed and calculated using the following formula. (2) Swelling degree: represents crosslinking density.

Accurately weigh the weight W2gr of the crosslinked vinyl chloride polymer that does not dissolve in THF that was collected during gel fraction measurement, and weigh it again at 40g.
After stirring for 1 hour with 0gr (7) THF, THF
As soon as the layer disappears, the weight of the filterable residue W3gr is accurately weighed and calculated using the following formula.

(3) Average particle size Measure with a microscope in the usual way.

The vinyl chloride polymer used in the method of the present invention is a vinyl chloride homopolymer or a vinyl chloride monomer that has only one active double bond, such as vinyl acetate,
A copolymer obtained by reaction with a comonomer such as ethylene, pyrene, styrene, acrylic acid, or methacrylic acid, and the copolymer can be produced by any method such as suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization. The copolymer may also be produced in the form of a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

Further, the average degree of polymerization is not particularly limited, but is preferably 1000 or more, particularly 1500 or more.
If the average degree of polymerization is less than 1000, the elasticity will be slightly inferior. The plasticizer used in the method of the present invention is not particularly limited as long as it is used for plasticizing vinyl chloride resin.

For example, phthalate plasticizers such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, dioctyl adipate, dioctyl azelate, sebacin Examples include fatty acid plasticizers such as dioctyl acid and methyl acetyl ricinoleate, phosphoric acid plasticizers such as tricresyl phosphate and trioctyl phosphate, and epoxy plasticizers such as alkyl epoxy stearate and epoxidized soybean oil. Also, two or more types are used. In order to further improve the effect of improving film stickiness, it is preferable to use a phthalic acid plasticizer in combination with a fatty acid plasticizer, especially dioctyl phthalate and dioctyl adipate because of their performance and because they are economically mass-produced. It is most suitable to use in combination. The proportion of the two in combination is not particularly limited, but from the viewpoint of improving stickiness, it is preferable to use a large amount of fatty acid plasticizer.
If the amount is too large, the original characteristics of the phthalic acid plasticizer tend to be lost and the miscibility with the polymer component tends to deteriorate.
When cold resistance is required, a large amount of fatty acid plasticizer may be intentionally used, but it is preferable to decide the ratio of both in consideration of the required amount of plasticizer, plasticization efficiency, etc. In a preferred embodiment, the fatty acid plasticizer is contained in an amount of 5 to 50% by weight, particularly 10 to 40% by weight, based on the total amount of plasticizer.
It is. The method of the present invention comprises the above-mentioned crosslinked vinyl chloride polymer,
A film is formed by calendering a composition containing a vinyl chloride polymer and a plasticizer as essential components.

The blending ratio of each is 5 to 9 for the crosslinked vinyl chloride polymer.
0 parts by weight, preferably 20 to 80 parts by weight, especially 30 to 7 parts by weight
The vinyl chloride polymer component is selected from the range of 0 parts by weight, while the vinyl chloride polymer component is selected from the range of 95 to 10 parts by weight, preferably 80 to 20 parts by weight, particularly 70 to 30 parts by weight. parts by weight, plus 20 to 200 parts of plasticizer
The composition is mixed in parts by weight, preferably in the range of 50 to 150 parts by weight. As the blending ratio of crosslinked vinyl chloride polymer increases, texture such as texture improves, but resistance to tearing tends to weaken.On the other hand, if the proportion of crosslinked vinyl chloride polymer becomes too small, physical properties such as tear resistance and tensile strength do not deteriorate. , the matting effect and texture, which are the most characteristic features of the present invention, become inferior, and the sliminess characteristic of vinyl chloride resin becomes stronger. In addition to the above-mentioned three components, this composition also includes heat stabilizers, ultraviolet absorbers, antioxidants, lubricants, flame retardants, etc., which are added to ordinary vinyl chloride resins.
Inorganic or organic fillers, dyes, pigments, etc. may be added as desired. In order to produce a vinyl resin film by the method of the present invention, first, the above-mentioned vinyl chloride polymer composition film is mixed with a lipon blender, a pen shell mixer, etc.
After uniformly mixing with a Banbury mixer, roll mill, kneading extruder, etc., and kneading uniformly with a mill roll set at a temperature slightly higher than the film processing temperature if necessary, the calender roll surface temperature is 140 to 200 °C and the calender speed is 5
The film is formed at a winding speed of 5 to 50 m/min, preferably 10 to 20 m/min, and a winding speed of 5 to 100 m/min, preferably 12 to 50 m/min.

The withdrawal rate is preferably 4 times or less, particularly 1.5 to 3 times. For example, when kneading is performed using a Banbury mixer, it is preferable to set the temperature of the Banbury mixer to a range of 100 to 180°C, and set the resin temperature to a range of from 150 to 210°C. The thickness of the film is adjusted to a desired thickness by adjusting the gap between calender rolls, processing temperature, stretching ratio, etc. The film thus obtained is sufficiently matte without being subjected to embossing or other treatments, has no stickiness, and has an extremely good texture.

However, such films tend to have slightly lower tear resistance than films made from ordinary vinyl chloride resins.
It is preferable to use it by laminating it with a base material such as an ordinary vinyl chloride resin film, other thermoplastic resin film, cellophane, paper, or woven fabric. The method of lamination is not particularly limited, and examples include a method of extrusion laminating vinyl chloride resin, other thermoplastic resin, etc. on the film after film forming, and a method of extrusion laminating a film obtained by the method of the present invention and a thermoplastic resin. Various methods are employed, such as a method of thermally bonding resin films, and a method of bonding a film obtained by the method of the present invention to cellophane, paper, woven fabric, or a resin film using an adhesive. Although it depends on the thickness of the base material, the laminate obtained in this way can be used even if heat treatment is performed after film forming, such as extrusion lamination or heat bonding with thermoplastic resin film. The matting effect, the effect of improving stickiness, and the texture are not impaired, and the physical properties such as tear strength and texture are excellent.

In the method of the present invention, a composition comprising a vinyl chloride polymer, a crosslinked vinyl chloride polymer, and a plasticizer is formed into a film, so the compatibility of each component is better than when other fillers are added. Even if the take-up rate is set to a high magnification, stable operation is possible without film breakage.

The resulting film is strong, matte, and non-sticky due to the incorporation of the crosslinked vinyl chloride polymer, and has an extremely good texture and touch. Even if the film is laminated with other base materials, the above-mentioned effects are not impaired at all. Therefore, the film or laminate obtained by the method of the present invention has a high-quality feel different from general vinyl chloride resin films, and has extremely high utility value as diaper covers and book covers that come in direct contact with the human body. It is also particularly useful as a light-shielding agricultural film. EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In the examples, "parts" represent "parts by weight."

Reference Examples The manufacturing method of the Shinahashi vinyl chloride polymer used in Examples and Comparative Examples is as follows.

Distilled water 60 m in a stainless steel autoclave with an internal volume of 31 m
0gr, suspending agent (hydroxypropyl methylcellulose 0.4% by weight/monomer sorbitan monolacalate 0
．． After adding a polymerization initiator (dioctyl peroxydicarbonate 0.05% by weight/monomer) and sealing the autoclave to completely remove the air inside, 300g of vinyl chloride monomer and 1% of diallyl phthalate were added. .2 gr was added and the temperature was raised to 53°C to carry out a polymerization reaction.

The autoclave internal pressure is 1kg/CO higher than the reaction pressure! When the temperature decreased by 1, unreacted monomers were removed and collected, and the resulting crosslinked polymer was dehydrated and dried. This crosslinked polymer had a gel fraction of 50%, a swelling degree of 30, and an average particle size of 40 μm. Examples 1 to 4, Comparative Examples 1 to 2 Crosslinked vinyl chloride polymer (4) obtained in Reference Example, non-crosslinked average degree of polymerization 2300 (B) and average degree of polymerization 1300 (
) vinyl chloride homopolymer, dioctyl phthalate (DOP) and dioctyl adipate (DOA) in the proportions (polymerized parts) shown in Table 1, further 0.5 part of lucium stearate, 2 parts of Ba-Zn stabilizer, 10 parts of calcium carbonate was sufficiently kneaded in a Banbury mixer set at a temperature of 150°C, and then transferred to a calender while kneading with a mill roll set at a temperature of 182°C to form a film with a thickness of 0.1 mm.

An L-shaped calender was used, the surface temperature of each roll was set at 180°C, the calender speed was 10.2 m/min, and the take-up speed was 25 m/min.
m/min. The quality of the obtained film was evaluated by the following method.

<Matte properties> Vinyl chloride resin films were observed with the naked eye, and their matte effects were classified into 5 grades, with ordinary vinyl chloride films (glossy films) being ranked 5th grade, and the degree of matting effect being graded 1 to 1 grade.

Surface unevenness> The degree of matteness was determined by measuring the number of unevenness on the surface of the vinyl chloride resin film using a surface roughness meter manufactured by Kosaka Laboratory per 10 mm length.

Tensile strength, elongation Measured based on JISK6732.

<Texture> Using a commercially available embossed polyvinyl chloride resin film as a reference, the hand feel of the sample film was compared, and the quality was expressed as ○ or ×.

Example 5 The vinyl chloride resin film used in Example 1 was layered with a normal vinyl chloride resin film (base material) and heated at a temperature of 150°C.
A laminated film was prepared by pressing at a pressure of 10 kg/CITl2 for 10 seconds.

The matte effect of the surface laminated with PVC resin film is
Almost the same as in Example 1, the number of surface irregularities is 78.
It was hot. From the results of Examples and Comparative Examples, the films obtained by the method of the present invention are slightly inferior to general vinyl chloride resin films in terms of strength, but have good matte properties and
It has excellent texture and texture, and has high utility value in fields of unconventional applications.

Claims (1)

[Claims] 1 Gel fraction 60% or less, swelling degree 5 or more, average particle size 70
After mixing and kneading 5 to 90 parts by weight of a crosslinked vinyl chloride polymer with a particle diameter of less than μ, 95 to 10 parts by weight of a non-crosslinked vinyl chloride polymer, and 20 to 200 parts by weight of a plasticizer,
A method for producing a vinyl chloride resin film, characterized by calendering at a temperature of °C.