Resin-coated sheet and method for producing same

Abstract

To solve the problem that a polyvinyl chloride-based resin-coated sheet for industrial material uses is exposed outdoors over a long period of time, and accordingly a liquid plasticizer blended in the polyvinyl chloride-based resin is gradually decomposed and degraded for many years, or tends to be transited to the surface; when such a situation occurs, the weight of the liquid plasticizer is reduced, thereby a feeling of the polyvinyl chloride-based resin layer tends to be gradually hardened; and when the liquid plasticizer is contained, the sheet surface tends be discolored.SOLUTION: A resin-coated sheet has a base fabric formed of a fiber material, and a resin-coated layer formed on at least one surface of the base fabric. The resin-coated layer contains a chlorine-based acrylic graft copolymer resin, a high-molecular plasticizer, and a straight vinyl chloride resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin-coated sheet and a method for producing the same. [Background technology]

[0002] As a polyvinyl chloride resin-coated sheet for industrial material applications, for example, a flexible sheet in which one or both sides of a fibrous base fabric are coated with a polyvinyl chloride resin layer is known (Patent Documents 1 to 3). Such resin-coated sheets are widely used in medium- to large-sized tents, tent warehouses, truck canopies, signboard backlits, etc. Such sheets exhibit the inherent advantages of polyvinyl chloride resins in terms of processability, economy, flame retardancy, etc. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2004-098697 A [Patent Document 2] Japanese Patent Application Publication No. 11-081158 [Patent Document 3] JP 2011-025518 A Summary of the Invention [Problem to be solved by the invention]

[0004] Since the sheets used for the above-mentioned purposes are exposed to the outdoors for a long period of time, the liquid plasticizer blended in the polyvinyl chloride resin is likely to gradually decompose, deteriorate, or migrate to the surface over the years. When this happens, the amount of liquid plasticizer decreases, which causes the texture of the polyvinyl chloride resin layer to gradually become hard. In addition, the presence of a liquid plasticizer also causes the surface of the sheet to easily discolor. [Means for solving the problem]

[0005] In order to solve such problems, the resin-coated sheet of the present invention has a base fabric formed from a fiber material and a resin coating layer formed on at least one surface of the base fabric, and is characterized in that the resin coating layer contains a chlorine-based acrylic graft copolymer resin, a high molecular weight plasticizer, and a straight polyvinyl chloride resin.

[0006] According to the resin-coated sheet of the present invention, the chlorine-based acrylic graft copolymer resin is preferably a copolymer of (A) a vinyl chloride monomer and (B1) a macromonomer having n-butyl acrylate in the main chain.

[0007] According to the resin-coated sheet of the present invention, it is preferable that the chlorine-based acrylic graft copolymer resin contains (A) a vinyl chloride monomer and (B1) a macromonomer having n-butyl acrylate in the main chain in a range of (A) / (B1)=85% by mass / 15% by mass to 75% by mass / 25% by mass.

[0008] According to the resin-coated sheet of the present invention, the chlorine-based acrylic graft copolymer resin is preferably a copolymer of (A) a vinyl chloride monomer and (B2) a macromonomer having in its main chain a polymer made of an ethylenically unsaturated monomer having a double bond.

[0009] According to the resin-coated sheet of the present invention, it is preferable that (B2) the macromonomer having in its main chain a polymer made of an ethylenically unsaturated monomer having a double bond is a poly(n-butyl acrylate) macromonomer having an acryloyl group at one end.

[0010] According to the resin-coated sheet of the present invention, the high molecular weight plasticizer is preferably at least one selected from an ethylene-vinyl acetate-carbon monoxide terpolymer and an ethylene-acrylic ester-carbon monoxide terpolymer.

[0011] According to the resin-coated sheet of the present invention, it is preferable that the high molecular weight plasticizer is contained in an amount of 10 to 120 parts by mass per 100 parts by mass of the chlorine-based acrylic graft copolymer resin.

[0012] According to the resin-coated sheet of the present invention, it is preferable that the straight vinyl chloride resin is contained in an amount of 1 to 100 parts by mass per 100 parts by mass of the chlorine-based acrylic graft copolymer resin.

[0013] The method for producing a resin-coated sheet of the present invention includes a base fabric formed of a fiber material and a resin coating layer formed on at least one surface of the base fabric, the resin coating layer including a chlorine-based acrylic graft copolymer resin, a high molecular weight plasticizer, and a straight polyvinyl chloride resin, the method comprising the steps of:

[0014] The chlorine-based acrylic graft copolymer resin is obtained by copolymerizing (A) a vinyl chloride monomer and (B1) a macromonomer having n-butyl acrylate in the main chain by a suspension polymerization method.

[0015] According to the method for producing a resin-coated sheet of the present invention, it is preferable to obtain a chlorine-based acrylic graft copolymer resin by copolymerizing (A) a vinyl chloride-based monomer and (B1) a macromonomer having n-butyl acrylate in the main chain in a ratio (A) / (B1) of 85% by mass / 15% by mass to 75% by mass / 25% by mass using a suspension polymerization method. Effect of the Invention

[0016] According to the resin-coated sheet of the present invention, flexibility can be imparted to the sheet without using a liquid plasticizer, and therefore the occurrence of a situation in which the plasticizer gradually decomposes, deteriorates, or migrates to the surface over many years, as occurs when a liquid plasticizer is used, can be prevented, and therefore the occurrence of a situation in which the amount of liquid plasticizer decreases, as a result of which the texture of the polyvinyl chloride resin layer tends to gradually become hard, as occurs when such a situation occurs, can be prevented. Also, discoloration of the sheet surface can be effectively prevented. The chlorine-based acrylic graft copolymer resin in the present invention has flexibility without using a plasticizer compared to vinyl chloride homopolymer resin, and therefore has the effect of reducing the use of high molecular weight plasticizers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The resin-coated sheet of the present invention has a base fabric formed of a fiber material and a resin coating layer formed on at least one surface of the base fabric. The resin coating layer contains a chlorine-based acrylic graft copolymer resin, a high molecular weight plasticizer, and a straight polyvinyl chloride resin.

[0018] The chlorine-based acrylic graft copolymer resin contained as the base material in the resin coating layer is preferably a copolymer of (A) vinyl chloride monomer and (B1) macromonomer having n-butyl acrylate in the main chain. In this case, it is preferable to contain (A) vinyl chloride monomer and (B1) macromonomer having n-butyl acrylate in the main chain in the range of (A) / (B1)=85% by mass / 15% by mass to 75% by mass / 25% by mass.

[0019] Alternatively, the chlorine-based acrylic graft copolymer resin contained as the base resin in the resin coating layer may preferably be a copolymer of (A) a vinyl chloride monomer and (B2) a macromonomer having in its main chain a polymer made of an ethylenically unsaturated monomer having a double bond. In this case, it is preferable that (B2) the macromonomer having in its main chain a polymer made of an ethylenically unsaturated monomer having a double bond is a poly(n-butyl acrylate) macromonomer having an acryloyl group at one end.

[0020] The resin coating layer contains a high molecular weight plasticizer as a plasticizer instead of the liquid plasticizer used in the known technology, thereby eliminating the above-mentioned disadvantages of containing a liquid plasticizer.

[0021] When the main component of the resin coating layer is the above-mentioned chlorine-based acrylic graft copolymer resin, the high molecular weight plasticizer is preferably at least one selected from ethylene-vinyl acetate-carbon monoxide terpolymer and ethylene-acrylic acid ester-carbon monoxide terpolymer. By using such a plasticizer, the resin coating layer mainly composed of the chlorine-based acrylic graft copolymer resin can be given the required flexibility without any problems.

[0022] In this case, it is preferable that the high molecular weight plasticizer is contained in an amount of 10 to 120 parts by mass per 100 parts by mass of the chlorine-based acrylic graft copolymer resin. If the content is less than 10 parts by mass, it is difficult to impart the required flexibility to the resin coating layer. On the other hand, if the content of the high molecular weight plasticizer exceeds 120 parts by mass, the strength of the obtained resin coating layer is reduced, and the resistance to abrasion and scratching tends to be insufficient.

[0023] The resin coating layer preferably contains 1 to 100 parts by mass of straight vinyl chloride resin per 100 parts by mass of chlorine-based acrylic graft copolymer resin. When the resin for constituting the resin coating layer is mixed and kneaded, if a liquid additive is used, the straight vinyl chloride resin can absorb the liquid additive to facilitate drying up. If the straight vinyl chloride resin content is less than 1 part by mass, it is difficult to obtain the required drying up effect. On the other hand, if the straight vinyl chloride resin content exceeds 100 parts by mass, the texture of the obtained resin coating layer becomes hard, and there is a tendency that a larger amount of high molecular weight plasticizer must be blended in order to impart a predetermined flexibility.

[0024] The base fabric constituting the resin-coated sheet of the present invention may be any fabric made of a fibrous material, such as glass fiber or other fibers.

[0025] The resin-coated sheet of the present invention can be preferably obtained by laminating a resin coating layer on a base fabric by a suitable method. In particular, when the chlorine-based acrylic graft copolymer resin of the resin coating layer is a copolymer of (A) a vinyl chloride monomer and (B1) a macromonomer having n-butyl acrylate in the main chain, the copolymer resin can be preferably obtained by copolymerizing the vinyl chloride monomer (A) and the macromonomer having n-butyl acrylate in the main chain (B1) by a suspension polymerization method.

[0026] Specifically, a chlorine-based acrylic graft copolymer resin can be preferably obtained by copolymerizing (A) a vinyl chloride-based monomer with (B1) a macromonomer having n-butyl acrylate in the main chain in a ratio (A) / (B1) range of 85% by mass / 15% by mass to 75% by mass / 25% by mass by a suspension polymerization method. EXAMPLES

[0027] <Example> A plain weave fabric (weaving density: warp threads 31 / inch, weft threads 30 / inch) using 1350 dtex glass multifilament yarns for the warp and weft was used as a glass cloth base fabric (mass 340 g / m2). This glass cloth base fabric was then immersed in a treatment solution containing 3% by mass of a fluorine-based water repellent agent and 1% by mass of a silane coupling agent, squeezed with a mangle, and heated under conditions of 190°C x 2 minutes to obtain a glass fiber base fabric entirely treated for water repellency with a fluorine-based compound.

[0028] As a chlorine-based acrylic graft copolymer resin, a resin obtained by copolymerizing (A) a vinyl chloride-based monomer and (B1) a macromonomer having n-butyl acrylate in the main chain by a suspension polymerization method (Plicktmer (registered trademark), GX grade, manufactured by Kaneka Corporation) was prepared.

[0029] Then, 100 parts by mass of this acrylic graft copolymer resin and ethylene- Acetic acid A raw material containing 30 parts by mass of vinyl-carbon monoxide terpolymer resin (Elvaloy (registered trademark) 741 manufactured by Dow Mitsui Polychemicals), 10 parts by mass of straight polyvinyl chloride resin, and other commonly used additives in appropriate amounts was mixed in a Henschel mixer, and the resulting mixture was kneaded to prepare a chlorine-based acrylic graft resin composition as a raw material for the resin coating layer.

[0030] Next, the above-mentioned layer of chlorine-based acrylic graft resin composition was laminated on the above-mentioned base fabric as a resin coating layer. That is, a urethane resin solution as an adhesive was applied to both sides of a water-repellent treated glass cloth base fabric using a knife coater, and heated under the conditions of 150°C x 2 minutes. The total amount of coating was 30g / m2 solid content on both sides. Then, a calendar-molded film of the above-mentioned chlorine-based acrylic graft resin composition having a thickness of 0.18mm was heat-pressed onto each of the urethane resin layers thus formed on both sides of the base fabric. As a result, a resin-coated sheet was obtained as a waterproof sheet having a thickness of 0.57mm and a mass of 840g / m2.

[0031] <Comparative Example> A resin composition for forming the resin coating layer was obtained. In detail, raw materials including 100 parts by mass of straight polyvinyl chloride resin, 32 parts by mass of DOP (bis(2-ethylhexyl) phthalate) which is a liquid plasticizer, 6 parts by mass of DOA (bis(2-ethylhexyl) adipate) which is also a liquid plasticizer, and other additives in appropriate amounts that are usually used were mixed in a single shell mixer, and the resulting mixture was kneaded to prepare a resin composition that is a raw material for the resin coating layer.

[0032] Other than that, the same procedures as in the above-mentioned Examples were carried out to obtain a resin-coated sheet as a Comparative Example.

[0033] <Evaluation> The samples were heated for a certain period of time at 80°C, which is expected to be the maximum temperature in the environment in which the sheet of the present invention will be used, i.e., placed in an 80°C atmosphere (using an oven set at 80°C) for a certain period of time, and the texture, heat loss, and sample appearance were evaluated at that time. Evaluations were made before the test, i.e., the blank, as well as after 1 week, 2 weeks, 3 weeks, and 4 weeks.

[0034] The texture was evaluated by measuring the bending resistance (mN) by the Gurley method defined in JIS L1096-2010. At this time, the bending resistance was measured for one side of the sample, i.e., the front side, and the other side of the sample, i.e., the back side.

[0035] The heat loss was calculated by cutting each sample into 10 cm squares, placing them in an oven at 80°C, measuring the mass of the blank, and then measuring the mass of each sample after a specified period of time. The rate of change from the blank was taken as the rate of weight loss.

[0036] The appearance was evaluated visually.

[0037] The evaluation results of the texture of the three samples (N1 to N3) of each of the examples and the comparative examples are shown in Table 1, and the evaluation results of the loss on heating are shown in Table 2.

[0038] [Table 1]

[0039] [Table 2]

[0040] As shown in Table 1, the texture of the examples was good, with almost no change even after 4 weeks at 80° C. In contrast, the texture of the comparative examples became hard after 4 weeks.

[0041] As shown in Table 2, the examples showed good results with almost no weight loss even after 4 weeks at 80° C. In contrast, the comparative examples showed a weight loss rate of about 7% after 4 weeks.

[0042] Regarding appearance, the Example had a slight reddish tinge after 4 weeks at 80° C. In contrast, the Comparative Example had a slight reddish tinge after 4 weeks at 80° C., and the degree of this reddish tinge was greater than that of the Example.

[0043] In summary, the sheets of the examples showed good results in terms of feel, heat loss and appearance after heating at 80° C., and were confirmed to be resin-coated sheets suitable for practical use.

Claims

1. The present invention has a base fabric formed of a fiber material and a resin coating layer formed on at least one surface of the base fabric, The resin coating layer contains a chlorine-based acrylic graft copolymer resin, a high molecular weight plasticizer, and a straight vinyl chloride resin, The resin-coated sheet is characterized in that the high molecular weight plasticizer is at least one selected from an ethylene-vinyl acetate-carbon monoxide terpolymer and an ethylene-acrylic ester-carbon monoxide terpolymer.

2. 2. The resin-coated sheet according to claim 1, characterized in that the chlorine-based acrylic graft copolymer resin is a copolymer of (A) a vinyl chloride-based monomer and (B1) a macromonomer having n-butyl acrylate in its main chain.

3. The resin-coated sheet according to claim 2, characterized in that the chlorine-based acrylic graft copolymer resin contains (A) a vinyl chloride-based monomer and (B1) a macromonomer having n-butyl acrylate in its main chain in a ratio of (A) / (B1) = 85% by mass / 15% by mass to 75% by mass / 25% by mass.

4. 2. The resin-coated sheet according to claim 1, characterized in that the chlorine-based acrylic graft copolymer resin is a copolymer of (A) a vinyl chloride-based monomer and (B2) a macromonomer having in its main chain a polymer made of an ethylenically unsaturated monomer having a double bond.

5. The resin-coated sheet according to claim 4, characterized in that the macromonomer (B2) having in its main chain a polymer composed of an ethylenically unsaturated monomer having a double bond is a poly(n-butyl acrylate) macromonomer having an acryloyl group at one end.

6. 6. The resin-coated sheet according to claim 1, further comprising 10 to 120 parts by weight of a high molecular weight plasticizer per 100 parts by weight of the chlorine-based acrylic graft copolymer resin.

7. 7. The resin-coated sheet according to claim 1, further comprising 1 to 100 parts by weight of straight vinyl chloride resin per 100 parts by weight of the chlorine-based acrylic graft copolymer resin.

8. When producing a resin-coated sheet according to any one of claims 1 to 7, The method for producing a resin-coated sheet is characterized in that the chlorine-based acrylic graft copolymer resin is obtained by copolymerizing (A) a vinyl chloride-based monomer and (B1) a macromonomer having n-butyl acrylate in the main chain by a suspension polymerization method.

9. 9. The method for producing a resin-coated sheet according to claim 8, characterized in that the chlorine-based acrylic graft copolymer resin is obtained by copolymerizing (A) a vinyl chloride-based monomer and (B1) a macromonomer having n-butyl acrylate in the main chain in a ratio (A) / (B1) of 85% by mass / 15% by mass to 75% by mass / 25% by mass by a suspension polymerization method.

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