JPH076135B2 - Filament canvas manufacturing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a filament canvas in which a soft polyvinyl chloride film is laminated on a woven or knitted fabric made of synthetic fiber multifilament yarn.

(Prior Art) Conventionally, a canvas made by coating a polyvinyl chloride resin on a base fabric woven and knitted using synthetic fiber filament yarns or spun yarns such as polyester, polyamide, and vinylon is well known. .

Regarding the coating process, various methods such as dipping, coating, topping, laminating, etc. have been proposed. In any of the processing methods, there is a problem in bonding the polyvinyl chloride resin and the woven or knitted fabric. In particular,
In the case of filament canvas, the anchoring effect cannot be expected unlike spun yarn, so it is necessary to make the texture of the woven or knitted fabric coarse, or to fabricate the fabric using flat yarns. For this reason, in order to improve the adhesiveness, it is manufactured by applying a thick polyvinyl chloride resin on the front and back of the base cloth, and then laminating a soft polyvinyl chloride film on the front and back of the base cloth. There is.

(Problems to be Solved by the Invention) However, in the case of the filament canvas produced by the above method, the strength of the woven or knitted fabric is low because the density of the woven or knitted fabric is low. To obtain the desired strength, the amount of polyvinyl chloride resin coated on the woven or knitted fabric is required. As a result, the weight of the canvas is large and only the texture is hard.

In particular, when a flat yarn is used for the constituent yarns of a woven or knitted fabric, it has an effect of strongly adhering, but it feels harder when it is paper-like.

In addition, in the case of a truck hood sheet, which is one of the main uses of canvas, a peel strength of 7 kg / inch or more and flexibility of the sheet are required from the viewpoint of physical properties. This is because the sheet is cracked due to wind-induced scratches, and rainwater penetrates to peel the laminate surface. For the above-mentioned applications, peel strength and flexibility are also important physical properties. .

The present invention has been made in order to solve the problems of the conventional filament canvas as described above, and provides a method for manufacturing a filament canvas having a high peeling strength and a soft texture.

(Means for Solving the Problems) The inventors of the present invention have arrived at the present invention as a result of intensive research to solve such problems.

That is, according to the present invention, a fluorine-based water / oil repellent agent is added to a woven / knitted fabric made of synthetic fiber multifilament yarn in a solid content of 0.
The first step of imparting 1 to 1% by weight, and then the viscosity obtained by adding a polyisocyanate compound to polyurethane 1000 to
Second step of applying 10000 centipoise adhesive solution to at least one side of the woven or knitted fabric and then drying, and then applying polyvinyl chloride paste resin to the adhesive coated surface of the woven or knitted fabric and then drying 3 steps, further, after heating the polyvinyl chloride paste resin to gel it,
The gist of the present invention is to provide a method for producing a filament canvas, which comprises a fourth step of laminating the woven / knitted fabric and a soft polyvinyl chloride film.

Hereinafter, the method of the present invention will be described in detail.

The synthetic fiber in the present invention is made of polyester, polyamide, polyolefin, polyvinyl alcohol, etc., and has the form of a long fiber filament yarn. In particular, polyester filament yarns are preferable from the viewpoint of strength and dimensional stability.

Next, the futonic water- and oil-repellent agent contains a polymer composed of perfluoroalkyl-containing methacrylate and perfluoroalkyl-containing acrylate as a main component. Since the critical surface tension of the perfluoroalkyl group in the side chain is extremely low, it has the property of being difficult to wet with liquids or solids with a greater intermolecular cohesive force. Representative examples of perfluoroalkyl-containing polymers used in the present invention are shown below.

CF ₃ (CF ₂ ) ₆ CH ₂ -A, CF ₃ (CF ₂ ) CH ₂ -M, (CF ₃ ) ₂ CH-A CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₂ CH ₂ CH ₃ ) CH ₂ CH ₂ -A (CF ₃ ) ₂ CH-M, CF ₃ (CF ₂ ) ₂ CH ₂ -A, HCF ₂ (CF ₂ ) ₃ CH ₂ -A A and M are acrylate and methacrylate repeating units, respectively. Represent Further, the fluorine-based water and oil repellent agent of the present invention includes those having acrylic amide, isocyanate, etc. in the main chain in addition to the above acrylate and methacrylate. The amount of the fluorine-based water and oil repellent attached to the woven or knitted material is 0.1 to 1% by weight in terms of solid content.
If it is less than 0.1% by weight, the water and oil repellency effect cannot be obtained on the surface of the woven or knitted fabric, and the adhesive is deposited on the entire surface of the woven or knitted fabric when the polyurethane adhesive is applied in the second step. Becomes hard. On the other hand, if it exceeds 1% by weight, the water / oil repellency of the surface layer of the woven or knitted fabric becomes too high and the peel strength becomes low. Therefore, the adhesion of the fluorine-based water and oil repellent agent to the woven or knitted material is 0.1 to 1% by weight, so that the adhesiveness is not hindered,
Moreover, since the adhesive does not penetrate the intersection of the woven and knitted fabrics,
A soft texture will be obtained.

Next, a polyurethane adhesive is applied to the woven or knitted fabric to which the fluorine-based water and oil repellent is applied. The polyurethane resin used is a high-molecular polymer obtained by reacting diisocyanate with two or more active hydrogen compounds, and is classified into two types, polyether type and polyester type, from the form of the raw material polyol, and the isocyanate is aromatic. It is classified into aromatic polyurethane and aliphatic polyurethane depending on whether it is composed of isocyanate or aliphatic isocyanate.

Usually, in the case of aromatic polyurethane, there is a problem that the benzene ring is turned into a quinoid by ultraviolet rays, which causes yellowing. This is because the presence of a nitrogen atom adjacent to the aromatic is an attack point for weathering deterioration, and this defect is overcome. For this purpose, a non-yellowing type urethane resin composed of an aliphatic isocyanate is preferably used. The Young's modulus of the polyurethane resin film is preferably in the range of 20-100 kg / cm ² . 20k
If it is less than g / cm ² , the film strength is weak and excellent adhesive strength cannot be obtained. On the other hand, if it exceeds 100 kg / cm ² , the texture becomes hard, which is not preferable.

The polyisocyanate compound has two or more isocyanate groups in one molecule, and is typically a prepolymer obtained by reacting a polyhydric alcohol with an excess of diisocyanate. It is roughly divided into the system type. Toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate and the like are typical aromatic compounds, and hexamethylene diisocyanate and the like are typical aliphatic compounds.

The amount of polyisocyanate compound added to the polyurethane resin is 0.5 to 2 relative to the weight of the polyurethane resin.
0% by weight is suitable. If the amount of polyisocyanate compound added is less than 0.5% by weight, the adhesion between the woven and knitted material and the polyvinyl chloride resin will be poor. On the other hand, if it exceeds 20% by weight, the cross-linking density of the polyurethane resin becomes too high, the feel becomes hard, and cracking tends to occur when used as a canvas. The amount of the adhesive solution applied to the woven or knitted fabric is preferably 5 to 100 g / m ² in terms of solid content. If it is less than 5 g / m ² , the affinity between the polyvinyl chloride resin and the woven or knitted fabric is not sufficient, and the adhesive strength becomes low. On the other hand, when it exceeds 100 g / m ² , the weight per unit area increases and the texture becomes hard.

Next, when the viscosity of the adhesive solution is less than 1000 centipoise, although the fluorine-based water and oil repellent agent is deposited on the base fabric, the fluidity of the adhesive solution is too high, so even at the intersection of the woven and knitted fabrics. Since the adhesive penetrates, only canvas with a hard texture can be obtained. On the other hand, if the viscosity exceeds 1000 centipoise, the fluidity of the adhesive solution becomes poor, so it is difficult to apply it evenly to the woven or knitted fabric, and when it is made into filament sailcloth, it has poor adhesion to soft polyvinyl chloride film. Will be things. The viscosity was 20
It was measured at ° C. Also, the method of applying the adhesive to the woven or knitted fabric is the padding method or the coating method.
As a drying method, a method usually used in a dyeing and finishing step can be adopted, and a dry heat treatment machine such as a roller dryer, a short loop dryer or a tenter can be used. However, if the drying temperature is too high, the crosslinking of the polyurethane resin proceeds too much. Therefore, in the present invention, it is preferable to perform the conditions at 80 to 150 ° C. for 1 to 5 minutes.

Subsequently, a polyvinyl chloride paste resin is applied to the base cloth subjected to the adhesive application process. The woven or knitted material is subjected to coating gelation treatment with a polyvinyl chloride paste resin, and the resin coating amount is preferably 50 to 200 g / m ² in terms of solid content. As a matter of course, the surface to be applied to the woven or knitted fabric is the surface to be laminated with the film.
The woven or knitted fabric is coated with resin under the drying condition for ~ 10 minutes.
Polyvinyl chloride paste resin consists of vinyl chloride paste resin, dialkyl phthalate plasticizer (eg, dioctyl phthalate, dibutyl phthalate, etc.) and diluent. These kneaded materials are applied by coating method or dipping method. To do. In addition, in order to impart flameproofness to the vinyl chloride resin, it is also possible to add an inorganic flameproofing agent such as antimony trioxide or antimony hydroxide.

The soft polyvinyl chloride resin to be laminated with the woven and knitted fabric in the fourth step is a mixture of the above polyvinyl chloride paste resin excluding the diluent with an ultraviolet absorber, an antioxidant, and a flameproofing agent mixed. It is made into a film by melt extrusion through a T-die.

The laminating process between the soft polyvinyl chloride film and the woven or knitted material is performed by heat-treating the woven or knitted material at 150 to 180 ° C to gel the polyvinyl chloride resin, and in this state, laminate with the soft polyvinyl chloride film. To process. The laminating conditions are temperature 160-180 ℃, pressure 10-50.
It is manufactured at a speed of 10 to 100 m / min using a calendering machine and a heat press machine at kg / cm ² .

The filament canvas produced by the above structure has strong adhesion, soft texture, lightweight, and high strength.

(Working) The present inventors consider the reason why the filament canvas of the present invention is soft in texture, excellent in adhesive strength, lightweight and high in strength.

First, by adding a fluorine-based water- and oil-repellent agent to a woven or knitted fabric made of synthetic fiber multifilament yarn, the polyurethane resin or polyvinyl chloride resin does not penetrate to the intersections of the woven or knitted fabric. The woven or knitted fabric can move to some extent at the intersection. As a result, the texture is soft, and the tear strength is less constrained by the yarns that make up the woven or knitted fabric, and the degree of freedom is large, so it is considered that the deformation stress can be sufficiently dealt with.

Next, regarding the application of the adhesive solution mainly composed of polyurethane resin to the woven or knitted fabric, the affinity of the synthetic fibers such as polyester, polyamide, vinylon and the polyvinyl chloride paste resin, especially the polyester fiber is the polyvinyl chloride resin. Since it has a poor affinity with, it is intended to improve the adhesiveness through a medium with a common affinity for both.

Therefore, the peel strength after lamination is improved by treating the woven or knitted fabric with the adhesive solution containing polyurethane resin as the main medium for both. However, if the intersection of the woven or knitted fabric is covered with the adhesive, the texture is hard and only a canvas with low strength can be obtained.

Therefore, by treating the woven or knitted fabric with a fluorine-based water / oil repellent agent in advance and then applying an adhesive, the perfluoroalkyl group in the side chain of the polymer constituting the fluorine-based water / oil repellent agent is extremely reduced. The low critical surface tension suppresses the penetration of the adhesive. Further, a fluorine-based water and oil repellent is usually an acrylic ester mainly composed of a polymer in which a perfluoroalkyl group is bonded as a side chain to a main chain of acrylic ester, methacrylic ester, acrylamide, isocyanate or the like. Since it is mainly composed of polyester, it has a great affinity for synthetic fibers such as polyester, polyamide, and vinylon, and also has excellent adhesiveness to the fibers.

In the present invention, the above-mentioned properties of the fluorine-based water- and oil-repellent agent are skillfully utilized, and the fluorine-based water- and oil-repellent agent within a specific range is used in view of the adhesiveness and the suppression of the permeation of the adhesive at the intersection of the woven and knitted fabrics. This is achieved by a combination of treatment with an oil agent and an adhesive solution mainly composed of a polyurethane resin having a specific viscosity range.

(Example) Hereinafter, the present invention will be described by way of examples.

Example 1 Polyester filament 1000 denier / 192 filament
The warp and weft are made of grit and the density is warp: 24 threads / inch
C, Weft: Weave a plain weave fabric of 24 threads / inch and
Machine heat set (185 ° C x 30 seconds) was performed. Next,
Fluorine-based water and oil repellent (trade name: Asahi Guard) AG-710, Ming
Seikagaku Co., Ltd. product, solid concentration 18%) 5% solution
Immerse the writing machine and process it with a mangle at a squeezing rate of 50%.
Dry at 120 ℃ and heat treat at 170 ℃ for 1 minute
It was Regarding the obtained water- and oil-repellent processed fabric, the following prescription 1
Glue the adhesive solution (viscosity 4000 centipoise at 20 ℃)
20g / m for each coating amount (solid content)²With double sided coattain
And dry it under the condition of 130 ℃ × 2 minutes.
I got a woven fabric.

[Prescription 1] Then, a polyvinyl chloride resin sol solution having the following formulation 2 was coated on both sides of the polyurethane adhesive-coated fabric with a knife coater at a coating amount (solid content) of 70 g / m ² each.

[Prescription 2] After drying at 130 ° C for 2 minutes, heat treatment at 170 ° C for 2 minutes, and then using a hot press machine,
Gelled polyvinyl chloride paste resin and soft polyvinyl chloride film (thickness 100μ) were used at a temperature of 165 ° C and a pressure of 25
Lamination was performed under the conditions of kg / cm ² and contact time of 3 seconds. The performance results of the obtained filament canvas are shown in Table 1.

Each performance in the table was measured by the following method.

(1) Heat-resistant peeling strength Measured after standing for 1 week under conditions of 40 ° C × 90% RH.

(2) Bending resistance: 45 ° cantilever method (the smaller the value, the softer) (3) Tear strength: Single tongue method Comparative Example 1 The plain weave fabric used in Example 1 was used, and a fluorine-based water and oil repellent agent was used. A filament sailcloth was produced in accordance with Example 1 without any treatment, from the polyurethane resin coating to the laminating with the soft polyvinyl chloride film. The performance results of the obtained filament canvas are shown in Table 1.

Comparative Example 2 Other than using the one prepared by changing the ethyl acetate of the diluent for the polyurethane resin adhesive solution of Formulation 1 in Example 1 to 100 parts and adjusting the viscosity of the adhesive solution to 20 ° C. and 300 centipoise. Under the same conditions as in Example 1, the polyester plain woven fabric was treated with a fluorine-based water and oil repellent agent and then laminated. The performance results of the obtained filament canvas are shown in Table 1.

As is apparent from Table 1, the filament canvas of the present invention had a high peel strength, a soft feeling, and an excellent tear strength.

(Effects of the Invention) The present invention relates to a method for manufacturing a filament canvas, which has the above-mentioned configuration, and has high peel strength,
And because you can get a soft filament canvas with a good texture,
It can be used in fields such as truck hood sheets.

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Claims (1)

[Claims] 1. A first step in which a fluorine-based water / oil repellent is applied in a solid content of 0.1 to 1% by weight to a woven or knitted fabric made of synthetic fiber multifilament yarn, and then a polyisocyanate compound is added to polyurethane. The second step of applying an adhesive solution having a viscosity of 1000 to 10,000 centipoise to at least one side of the woven or knitted fabric and then drying it, and then applying a polyvinyl chloride paste resin to the adhesive coated side of the woven or knitted fabric. After that, the method further comprises a third step of drying, and a fourth step of heating the polyvinyl chloride paste resin to gel it and then laminating the woven and knitted fabric and the soft polyvinyl chloride film. A method for manufacturing a filament canvas.