JPH06116876A - Production of pvc leather cloth - Google Patents

Abstract

PURPOSE:To produce PVC leather cloth having excellent softness and strength, high abrasion resistance, excellent compression recovery and light weight by calendering process in high efficiency. CONSTITUTION:A composition containing 100 pts.wt. of a PVC resin, 30-90 pts.wt. of a plasticizer, 10-50 pts.wt. of hollow glass microspheres and 1-10 pts.wt. of an acrylic resin is kneaded to obtain a PVC compound. The compound is rolled with a hot calender roll to form a sheet by calendering and topped on base cloth to form a laminated PVC resin layer containing the hollow glass microspheres uniformly dispersed in the resin layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing vinyl leather, which is capable of obtaining lightweight leather.

[0002]

2. Description of the Related Art Conventionally, generally used vinyl leather is roughly classified into ordinary leather (also called non-foamed leather) and foamed leather depending on its structure. Of these, non-foamed leather uses vinyl chloride resin,
The heavy weight is a major drawback. For example, vinyl leather used for bags and the like is required to have a reduced weight. Therefore, as vinyl leather used for golf bags, vinyl chloride (P
VC) based resin to 100 parts by weight of plasticizer 30 to 90
And a foaming agent of 2 to 7 parts by weight, and a stabilizer of 0.5 to 10 parts by weight, and a foaming ratio of 150 to 70.
There is one in which a 0% foamed layer is laminated, and if necessary, a non-foamed layer of vinyl chloride resin and / or a surface treatment layer is laminated on the foamed layer. Further, as described above, as one of the methods for obtaining a lightweight leather, a method of incorporating a foaming agent and foaming is also adopted.

On the other hand, as another means for reducing the weight,
It is also conceivable to add an inorganic filler composed of a hollow body to the vinyl chloride resin. As a technology using a hollow body,
As a wall covering material, a resin composition prepared by blending a hollow inorganic filler, a foaming agent and a plasticizer into a synthetic resin mainly composed of polyvinyl chloride is coated on a substrate such as paper or cloth to obtain an arbitrary unevenness. There is vinyl leather made by foaming after patterning. In this vinyl leather, the inorganic filler composed of the hollow body is partly destroyed when an uneven pattern is applied, and an extremely deep uneven pattern is provided. In addition, when foaming this, the expansion of the concave portion causes a thickness reduction only in the broken portion of the filler and the expansion coefficient becomes smaller than that of the convex portion, so that there is a more faithful and clear three-dimensional unevenness than ever before. It is supposed to form a pattern.

[0004]

As described above, if the addition ratio of the foaming agent is increased and the expansion ratio is increased in order to reduce the weight of the vinyl leather, the physical strength of the vinyl leather is significantly lowered. , The recovery of dents generated when an external force is applied remarkably deteriorates, the surface appearance becomes rough and the appearance remarkably deteriorates.Therefore, there is a limit to the expansion ratio of the foamed vinyl leather that can be put to practical use, There was a limit to the weight reduction of vinyl leather by increasing the expansion ratio.

In addition, the latter vinyl leather in the wall covering is intended to obtain a clear uneven pattern, and the inorganic filler of the hollow body is destroyed during the processing,
Since the content of the hollow body that is effective for weight reduction is reduced, sufficient weight reduction cannot be achieved. At the time of making this wall covering material, a PVC paste containing a hollow body was used.
Apply it to a base cloth such as paper or cloth, heat it into a gel, or apply a PVC paste containing a hollow body to release paper,
A so-called paste method is employed, in which this is heated and gelled, and then a base cloth fed from above is attached and the release paper is peeled off. However, in this paste method, since the hollow body floats on the upper surface of the paste between the time when the PVC paste is applied on the base cloth or the release paper and the time when it is gelled by heating, the hollow body in the thickness direction of the PVC layer Non-uniform distribution (when using release paper, it is unevenly distributed on the side where the base cloth is attached, and when directly coated on the base cloth, it is unevenly distributed on the opposite side to the surface where it is attached). It is not possible to obtain a practical and lightweight vinyl leather that not only does not satisfy both the improvement of the physical strength and the improvement of the physical strength at the same time, but also the recovery of the dent can be improved.

On the other hand, conventionally, it is generally known that processing a PVC composition containing a fragile glass hollow body by a calendering method breaks the glass hollow body during kneading and calendering the PVC composition. There is a common belief that the calendering method was not used in the production of vinyl leather containing glass hollow bodies. The present inventors attempted to obtain vinyl leather by processing a PVC composition containing a glass hollow body by a calendering method, but the hollow glass body was often destroyed, and banks were formed uniformly during calendering. However, a good lightweight vinyl leather could not be obtained.

The inventors of the present invention have solved the above-mentioned problems of the prior art, have less breakage of the hollow bodies, have a uniform distribution of the hollow bodies, and are excellent in flexibility and strength, and are also lightweight in terms of wear resistance. As a result of diligent research aimed at providing a method for producing vinyl leather capable of producing various vinyl leather, surprisingly, by adding a small amount of an acrylic resin to a PVC composition blended in a glass hollow body, a calender Not only is the bank uniformly formed during processing, but the glass hollow body is less destroyed, and it is possible to obtain a lightweight vinyl leather in which the glass hollow body is uniformly dispersed in the vinyl chloride resin layer. The present invention has been completed under the heading.

[0008]

The present invention is based on 100 parts by weight of a vinyl chloride resin, 30 to 90 parts by weight of a plasticizer, 10 to 50 parts by weight of glass micro hollow spheres, and 1 to 10 parts by weight of an acrylic resin. The PVC compound prepared by kneading the composition containing is rolled by a calender roll heated by a calender method to be dispensed into a sheet, and the glass microhollow spheres are uniformly dispersed by topping on a base cloth. Another object of the present invention is to provide a method for producing vinyl leather, which comprises laminating and forming a vinyl chloride resin layer.

The method for producing vinyl leather of the present invention is shown in FIG.
As shown in FIG. 2, a composition containing a vinyl chloride resin, a plasticizer, glass micro hollow spheres, and an acrylic resin is kneaded with a kneading roll 11 to obtain PVC compound C, which is then placed on a calendar roll 13 heated by a conveyor 12. Send in. Therefore, the PVC compound C initially having a thickness of about 1 cm is rolled to a thickness of 0.2 to 0.3.
In the case of containing a foaming agent, the base fabric 20 and the laminating roll 14 fed from below are pressed together to be integrated and wound through the cooling roll 15, and when the foaming agent is contained, In a foaming furnace 16, the foamed resin is heated and foamed at 200 to 220 ° C. and is wound through a cooling roll 17 to form and laminate a vinyl chloride resin layer 30 in which glass micro hollow spheres 40 are uniformly dispersed as shown in FIG. Vinyl leather 10
Is what you get. When it is desired to give the vinyl chloride resin layer 30 a concavo-convex pattern, the vinyl chloride resin layer 30 is further inlined through the embossing roll 18. Here, the PVC compound C is kneaded by the kneading roll 11 or rolled by the calender roll 13 to be a sheet, and the glass micro hollow spheres 40 used as the filler are hollow powdery spheres and have a high strength. Since it is also large and uses an acrylic resin in combination, it is not destroyed and is uniformly dispersed in the vinyl chloride resin layer 30.

In the present invention, vinyl leather 10
The base fabric 20 used for is a so-called vinyl leather base sheet, and for example, a woven fabric, a knitted fabric, a non-woven fabric or the like can be used, and the material thereof is cotton, staple fiber, polyester fiber, polyamide fiber. Any fiber such as natural fiber such as vinylon fiber and synthetic fiber may be used.

The vinyl chloride resin used as the main component of the vinyl chloride resin layer 30 in the vinyl leather 10 of the present invention includes polyvinyl chloride (vinyl chloride homopolymer), vinyl chloride and other monomers. , For example, copolymers with ethylene, vinyl acetate, vinyl ether, maleic acid ester, (meth) acrylic acid, (meth) acrylic acid ester, etc., as well as those containing a mixture of polyvinyl chloride and other polymers, The average degree of polymerization of the vinyl chloride resin used is 70 from the viewpoint of calender processability.
It is 0 to 2,000, preferably 700 to 1,500.

Examples of the plasticizer contained in the vinyl chloride resin include dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, didodecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, dihexyl phthalate, diisononyl phthalate, dioctyl adipate, Diisodecyl adipate, dibutyl sebacate, dioctyl sebacate, tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, diphenyl cresyl phosphate, trimellitic acid ester plasticizer, epoxy plasticizer Agents, polyester-based polymer plasticizers and the like can be used. The plasticizer is added in an amount of 30 to 90 parts by weight, preferably 40 to 80 parts by weight, based on 100 parts by weight of the vinyl chloride resin. These plasticizers can be used alone or in combination of two or more kinds.

As the acrylic resin used in the present invention, any thermoplastic acrylic resin can be used. The amount added is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If it is less than 1 part by weight, it is impossible to calender a PVC composition containing glass micro hollow spheres, while if it is used in excess of 10 parts by weight, the improvement of the effect is poor.

Further, the glass micro hollow spheres 40 blended in the vinyl chloride resin as a filler are a general term for micro hollow spheres containing silicon dioxide as a main component and having a hollow inside. The true density of the glass micro hollow spheres 40 is preferably 0.2 to 0.6 g / cm ³ , more preferably 0.3 to 0.5 g / cm ³ , and the strength is preferably 10.
0 to 400 g / cm ² , more preferably 150 to 35
It is 0 kg /. If the true density is less than 0.2 g / cm ³ or the strength is less than 100 kg / cm ² , the walls of the micro hollow spheres become too thin and are easily broken during calendering. On the other hand, if the true density exceeds 0.6 kg / cm ³ or the strength exceeds 400 kg / cm ² , the wall of the micro hollow sphere becomes too thick and heavy, and the effect of weight reduction of the present invention can be achieved. There will be no.

A specific example of the glass micro hollow sphere 40 is CEL-STAR manufactured by Asahi Glass Co., Ltd.
The particle size range manufactured and sold under the product name is 10-120μ
m of pure white powder-like round and minute hollow spheres. It has light weight and heat insulating properties that are not found in general fillers, and is inorganic and therefore heat resistant. This CEL-STA
R is part number Z-27, Z-36, Z-39, Z-42,
There are types such as Z-45, but the strength of Z-27 is 50k.
g / cm ² is too low, so the true density is 0.33 to 0.4
It is preferable to select an appropriate product number from Z-36 to Z-45 having a strength of 8 g / cm ³ and a strength of 150 to 350 kg / cm ² in accordance with a desired application and condition.

The amount of the glass micro hollow spheres 40 added is
It is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the vinyl chloride resin, and if it is less than 10 parts by weight, the effect of weight reduction and compression recovery are poor.
The vinyl leather obtained even if it is used in an amount of more than 0 parts by weight does not lighten proportionally, and there is a fear that the spheres may be destroyed by friction between the spheres during calendering, which may impair the effect of weight reduction. , The banks may become uneven.

The vinyl leather 10 of the present invention is characterized in that the glass micro hollow spheres 40 are uniformly dispersed in the vinyl chloride resin 30. in this way,
Since the glass micro hollow spheres 40 are uniformly dispersed, the glass micro hollow spheres are less broken during embossing, and the compression recovery property is excellent.

Further, as the foaming agent contained in the vinyl chloride resin, if necessary, a usual one such as azodicarbonamide or dinitrosopentamethylenetetramine can be used. Among them, azodicarbonamide is preferable. The amount of addition is 2 to 7 parts by weight, preferably 3 to 4 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If it is less than 2 parts by weight, foaming is not sufficient, while it exceeds 7 parts by weight. In addition to the foaming ratio increasing too much and the processing workability deteriorates, not only the cells become rough and foaming failure tends to occur, but the physical strength of the resulting vinyl leather decreases, and the surface becomes rough, which can be put to practical use. Absent. The expansion ratio (the thickness change rate between the sheet thickness before foaming and the sheet thickness after foaming) of the vinyl chloride resin composition with this foaming agent is preferably 150 to 700%, more preferably 200 to 600%. Is.

In the composition constituting the vinyl chloride resin 30 of the present invention, other additives such as a stabilizer, a cell conditioner, a colorant, a mildew proofing agent, a lubricant, and the glass microhollow are used. Fillers other than spheres can be added.

Examples of the stabilizer include tin-based stabilizers such as dibutyltin laurate and metal soaps such as zinc stearate and calcium stearate. As the stabilizer, a stabilizer capable of suppressing foaming of the foaming agent may be used in combination. Examples of such a stabilizer having an effect of suppressing foaming include tin-based, barium-based, calcium-based, barium-zinc-based, low zinc content, and calcium-zinc when azodicarbonamide is used as the foaming agent. A system having a low zinc content is used. The amount of such a stabilizer added is preferably 0.1% based on 100 parts by weight of the vinyl chloride resin.
5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight,
If it is less than 0.5 parts by weight, the thermal stability of the vinyl chloride resin will be poor, while if it is more than 10 parts by weight, not only quality problems such as bloom and bleed are likely to occur, but also the price becomes high, which is not preferable.

The cell conditioner prevents the surface of the vinyl chloride resin 30 from being roughened by uniformizing the foaming of the vinyl chloride resin composition with the foaming agent. Examples of the cell conditioner include ethylene. -Vinyl acetate copolymer resin or the like can be used. The amount of the cell regulator added is 0.1 to 10 parts by weight, preferably 0.8 to 8 parts by weight, based on 100 parts by weight of the vinyl chloride resin, and if less than 0.1 parts by weight, the foaming is uniform. Therefore, the effect of preventing roughening of the surface of the vinyl chloride resin 30 is small, and when it exceeds 10 parts by weight, the cost may be increased and the productivity may be deteriorated.

A skin layer 50 and / or a surface treatment layer 60 may be laminated on the vinyl chloride resin layer 30 of vinyl leather obtained by the manufacturing method of the present invention as shown in FIG. The skin layer 50 can be formed of a non-foaming PVC composition obtained by removing the foaming agent from the PVC composition. When both the skin layer 50 and the surface treatment layer 60 are laminated, the skin layer 50 is formed on the vinyl chloride resin layer 30, and the surface treatment layer 60 is formed on the skin layer 50. Further, when the urethane resin is used for the surface treatment layer 60, not only the vinyl leather disappears the grain, but the phenomenon such as the grain flow and the gloss change does not occur, and a high-grade feeling is obtained.
The urethane-based resin used for the surface treatment layer 60 is the same urethane-based resin as the vinyl chloride-based resin layer 30 and containing additives such as colorants, stabilizers, and fillers. Good.

[0023]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 100 parts by weight of vinyl chloride resin (average degree of polymerization: 1,100
30 parts by weight of PVC and 70 parts by weight of PVC having an average degree of polymerization of 800), 70 parts by weight of a plasticizer (dioctyl phthalate), glass micro hollow spheres 40 (CE
L-STAR) 30 parts by weight, acrylic resin 6 parts by weight, stabilizer (Va-Zn composite stabilizer) 3 parts by weight, and pigment 5 parts by weight were mixed and kneaded into the PVC compound, and the calendar device shown in FIG. A vinyl chloride resin layer in which a CEL-STAR as shown in FIG. 2 is uniformly dispersed while being dispensed into a sheet having a thickness of 0.2 to 0.3 mm and topped on the base fabric 20. Vinyl leather 10 having 30 laminated thereon was obtained. The PVC compound is rolled by the calender rolls 13 and dispensed into a sheet, but since the acrylic resin is used together, the banks are uniformly formed and dispensed to a uniform thickness, and the filling is performed. CEL-STAR used as an agent was not easily broken, and was uniformly dispersed in the vinyl chloride resin layer 30. Thus, in this vinyl leather 10, P
The specific gravity of the VC compound (at the time of kneading) is 0.90 to 0.
It was 97, which was about three-fourths lighter than the conventional one.

Comparative Example 1 A PVC compound, which was mixed and kneaded in the same manner as in Example 1 except that an acrylic resin was not used together, was used to calender 0.2 to 0.3 mm in thickness using a calender device shown in FIG. Was divided into sheets and topped on the base cloth 20 to obtain vinyl leather. The PVC compound is rolled by a calender roll 13 and dispensed into a sheet, but since acrylic resin is not used together, the bank is not formed uniformly, and the PVC compound is provided on the opposite side of the calender bottom roll. Not only becomes uneven in thickness of the vinyl chloride resin layer formed on the base fabric when the base fabric is topped, but also the sauce on the opposite side of the bottom roll is chlorinated by the above-mentioned topping. In some cases, the vinyl-based resin layer sometimes drooped down, so that not only good vinyl leather could not be obtained, but also the glass micro hollow spheres were often broken.

Comparative Example 2 Except that the amount of acrylic resin used was 0.5 parts by weight,
The PVC compound mixed and kneaded in the same manner as in Example 1 was used to obtain a thickness of 0.1% by using the calender device shown in FIG.
A sheet-shaped piece of 2 to 0.3 mm was dispensed and topped on the base fabric 20 to obtain vinyl leather. In addition,
The PVC compound is rolled by a calender roll 13 and dispensed into a sheet, but since the amount of the acrylic resin used is too small, the banks are not uniformly formed as in Comparative Example 1, and the bottom roll of the calender is The PVC compound will flow (drip) to the opposite side, and not only will the thickness of the vinyl chloride resin layer formed on the base fabric become uneven when it is topped on the base fabric, but also the sagging on the opposite side of the bottom roll will occur. However, not only good vinyl leather could not be obtained, but also the glass micro hollow spheres were often broken.

As is clear from the examples and the comparative examples 1 and 2, only the examples of the present invention can produce a lightweight vinyl leather excellent in quality using glass micro hollow spheres by the calendar method. . Since Comparative Examples 1 and 2 do not use a specific amount of acrylic resin in combination, when a PVC compound containing glass micro hollow spheres is rolled by a calender roll, a uniform bank is not formed,
It is not possible to obtain a lightened vinyl leather laser with good quality.

[0027]

EFFECTS OF THE INVENTION According to the present invention, a specific amount of an acrylic resin is blended in a vinyl chloride resin composition containing light weight and high strength glass micro hollow spheres.
Even when the composition is dispensed into a sheet by using a calendering method, a bank is uniformly formed, and the glass micro hollow spheres are hardly broken, and a vinyl leather in which the glass micro hollow spheres are uniformly dispersed is obtained. Is possible,
It is possible to efficiently produce a lightweight vinyl leather excellent in flexibility and strength, which is excellent in abrasion resistance and compression recovery, by a calendar method.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a main part of a calendar device used in a method for producing vinyl leather according to an embodiment of the present invention.

FIG. 2 is a partially enlarged sectional view of vinyl leather obtained by the present invention.

[Explanation of symbols]

 10 Vinyl Leather 20 Base Fabric 30 Vinyl Chloride Resin Layer 40 Glass Micro Hollow Sphere 13 Calendar Roll 16 Foaming Furnace C PVC Compound

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
Plasticizer 30-90 parts by weight, glass micro hollow sphere 10-5
A PVC compound prepared by kneading a composition containing 0 part by weight and 1 to 10 parts by weight of an acrylic resin is rolled by a calender roll heated by a calendering method to be dispensed into a sheet, and is also placed on a base cloth. Toppings,
A method for producing vinyl leather, which comprises laminating and forming a vinyl chloride resin layer in which the glass micro hollow spheres are uniformly dispersed.