JPH0367650A - Marking sheet - Google Patents

Abstract

PURPOSE:To obtain a sheet having high anti-staining properties, high marking agent release strength and practical durability as industrial materials such as an interior reinforcing material or an electric material by coating base cloth with a polyvinyl chloride resin and applying an acrylic resin and fluoroplastic on said resin to expose 9% or more of the acrylic resin. CONSTITUTION:A resin coated sheet is formed by coating base cloth with a polyvinyl chloride resin and further coating said resin with an acrylic resin and fluoroplastic. At this time, the acrylic resin is exposed to the surface of the sheet in an amount of 9% or more, 9-90% or 20-50%. the m.p. or gelling temp. of the acrylic resin and fluoroplastic is 200 deg.C or lower and the light transmissivity of the sheet is 5% or more. The surface layer of the sheet has such a three-layer structure that an outer layer mainly consists of 9% or more of the acrylic resin and 91% or less of the fluoroplastic, a middle layer consists of 70% more of the fluoroplastic and 30% or less of the acrylic resin and an inner layer consists of 30% or less of the fluoroplastic and 70% or more of the acrylic resin.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a marking sheet used for tents, backlits, signboards (illuminating boards), pool covers, warehouses, oil fences, curing sheets, etc. It is used for industrial materials such as interior reinforcement materials and electrical materials.

<Prior art> In recent years, sheets made by laminating polyvinyl chloride resin (hereinafter referred to as PVC resin) as a coating on a base fabric knitted and woven from synthetic fibers, glass yarn, etc. have been used in tents, battalits, lighting boards, etc. ing.

Required properties in these application fields include stain resistance, printability, durability, etc., and in order to meet these requirements, PVC
A sheet in which the surface of a resin is coated with an acrylic resin, a laminate with a fluororesin or a fluororesin film, etc. are provided. However, sheets coated with acrylic resin have good printing suitability for screen printing, thermal transfer, etc., but have low peeling strength and poor stain resistance when used with cal paste.
Although fluororesin film laminated films have excellent stain resistance, they have poor suitability for printing such as screen printing and thermal transfer, and cannot be used for thermal transfer.

<Purpose of the Invention> As a result of intensive studies in view of the problems of the prior art, the present inventor has solved the above problems by combining fluororesin and acrylic resin and exposing 9% or more of the acrylic resin on the sheet surface. We have found that this problem can be solved and have led to the present invention.

<Structure of the Invention> That is, the present invention provides: (1) A resin-coated sheet comprising a base fabric coated with a polyvinyl chloride resin, and an acrylic resin and a fluororesin coated on the resin, in which 9% or more of the acrylic resin is A marking sheet characterized by displaying.

(2) The marking sheet according to claim (1), wherein 9 to 90% of the acrylic resin is exposed.

(3) The marking sheet according to claim (1), wherein 20 to 50% of the acrylic resin is exposed.

(4) The marking sheet according to any one of claims (1) to (3), wherein the acrylic resin and the fluororesin have a melting point or gelling temperature of 200°C or less.

(5) Claim (1) that the light transmittance of the sheet is 5% or more.
The marking sheet according to any one of (4) to (4).

(6) The surface layer of the sheet has a three-layer structure, with the outer layer mainly consisting of 9% or more acrylic resin and 91% or less fluororesin, the middle layer consisting of 70% or more fluororesin and 30% or less acrylic resin, and the inner layer (laminated to the PVC resin layer). layer) is 30% fluororesin
Claims (1) to (5) below, in which the content is 70% or more of acrylic resin.
) is a marking sheet according to any one of the above.

Although the fibers used for the base fabric are not particularly limited, it is preferable to use multifilaments made of polyester, polyamide, aramid, polyvinyl alcohol, glass, or the like.

The combination of fluororesin and acrylic resin may be a mixture of fluororesin and acrylic resin, the acrylic resin layer may be dotted on the surface of the fluororesin layer, or the entire surface may be covered in the form of a film. good. The mixture of acrylic resin and fluororesin may be an alloy, a copolymer, or a hot melt mixture.

Other mixed and integrated ones may also be used. However, the amount of acrylic resin exposed on the sheet surface is 9% or more, preferably 20% or more.

If it is less than 9%, the ink adhesive strength during screen printing or thermal transfer will be weak and will not be practical.

When pasting a cull, the adhesive strength with the adhesive on the back of the cull is improved.

Note that it is preferable that the resin layer (inner layer) in contact with the PVC resin layer be rich in acrylic resin in order to improve adhesive strength by thermal lamination, so it is desirable that the resin layer is at least 30% acrylic resin.It is desirable that the outer layer be rich in acrylic resin and the middle layer be rich in fluororesin. A three-layer structure with a rich and inner layer rich in acrylic resin is best.

Preferably, a film-like material is laminated to a vinyl chloride resin layer, that is, the outer layer is 9% or more of acrylic resin and 91% or less of fluororesin, and the middle layer is 30% or less of acrylic resin and 70% or more of fluororesin, preferably acrylic. The resin content is 9% or less and the fluororesin content is 91% or more. The inner layer (the surface to be laminated with the PVC resin layer) is made of acrylic resin of 30% or more and fluororesin 70.
% or less is preferable.

If the fluororesin content of the middle layer is less than 70%, the plasticizer etc. in the PVCVII fat may bleed out over a period of 5 to 10 years, making it easy to stain.

If the inner layer contains less than 30% acrylic resin, the adhesive strength with the PVC resin during hot lamination will be weak.

Since it is desirable that the peel strength is 3 kg/3 cm or more, it is preferably 50% or more.

In addition, the fluororesin content is 4.5 g/M or more in terms of unit weight, and 9 g/r in total weight of acrylic resin and fluororesin.
rf or more is preferable. At 4.5 g/rrf of fluororesin, the antifouling durability effect is insufficient, and the total weight is 9 g.
If it is less than /rrf, the strength of the film will be low and the surface will be easily scratched, resulting in poor antifouling durability.

The mixing ratio of fluororesin and acrylic resin in the surface layer is acrylic resin: 9 to 90%, fluororesin: 90 to 1% by weight.
0% is desirable. Note that the layer made of fluororesin and acrylic resin may have a multilayer structure with different mixing ratios of fluororesin and acrylic resin (for example, the surface layer 10μ is made of 20% acrylic resin and 80% fluororesin, and the inner layer 20μ is made of 20% acrylic resin and 80% fluororesin.
is a multilayer structure sheet in which a two-layer structure film made of 80% acrylic resin and 20% fluororesin is laminated to a PVC resin layer).

Note that it is preferable to use a layer containing at least 9%, preferably 50% or more of acrylic resin so as to adhere to the PVC resin layer. If it is less than 9%, the adhesive strength with the PVC resin layer is insufficient and peeling is likely to occur.

In addition, when a film layer consisting of a single fluororesin is inserted in the middle, the thickness is preferably 2 to 25 μm, and it is desirable that the surface layer is coated with an acrylic resin layer of 2 to 10 μm. If the thickness of the fluororesin layer exceeds 25μ, the sheet becomes hard and is not practical. 2
If it is less than μ, it is difficult to produce a uniform film and high quality cannot be obtained. The effects of such a laminate are that the fluororesin layer prevents the plasticizer from bleeding out from the vinyl chloride resin, and the acrylic resin layer on the surface improves printability. The acrylic resin and fluororesin layer on the surface makes it difficult for external dirt to adhere. When there are many acrylic resin layers on the surface, printability improves, but the stain prevention effect is slightly lower than that of fluororesin alone, but the stain resistance is sufficient to withstand use.

On the other hand, fluororesin laminate products were considered difficult to weld, but by using a fluororesin and acrylic resin or a mixture thereof with a melting point or gelling temperature of 200°C or lower, preferably 180°C or lower, It was discovered that welder processing is possible.

For example, products laminated with polyvinyl fluoride resin (melting point 210°C) on the surface (Tedra Film 012μ, 25μ, sold by Pont) are known, but cholera cannot be welded.

However, polyvinylidene fluoride resin (melting point 160~
180° C. and methyl methacrylate resin, or a film containing a single layer of polyvinylidene fluoride resin and having a total thickness of 50 μm or less, which is silently bonded, can be fully welded.

Furthermore, sheets made of woven or knitted polyester fibers laminated with transparent PVC resin or semi-transparent PVC resin on both sides have been used as transparent tents, but these tents get very dirty and cannot withstand long-term use. Therefore, by combining the above-mentioned transparent sheet with the present invention, it was possible to create a transparent tent that is resistant to staining and has a lasting light-transmitting property. In other words, the light transmittance (
By using a transparent sheet having a surface coated with a fluororesin/acrylic resin mixed sheet having a JIS K7105 of 5% or more, preferably 20% or more, a transparent sheet with high antifouling durability can be obtained.

<Effect of the invention> The present invention has the following effects.

1) By providing a layer consisting of acrylic resin and fluororesin on the surface layer and making the acrylic resin exposed at least 9% or more, screen printing, thermal transfer, cal pasting, etc. are possible, and stain resistance and marking are achieved. This is a practical and durable sheet with high adhesive peeling strength.

2) It is generally believed that welding is difficult when a fluororesin is included, but the melting point or gelation temperature of the acrylic resin and fluororesin should be set to 200℃ or less, preferably 130 to 18℃.
By applying a temperature of 0°C to the surface layer, a welding processable sheet for marging was obtained.

3) Conventional marking sheets had a sharp decline in light transmission due to surface stains, but the present invention is a marking sheet with extremely high light transmission durability.

<Example> The method for manufacturing a marking sheet of the present invention will be described below using an example.

Evaluation characteristics in Examples were measured according to the following method.

(1) Light transmittance According to JIS K 7105.

(2) Marking material peeling test JIS Z 0237
According to (0.5Kg/inch or more is actually usable>(1
(80° Peeling Method) (3) Durability Acceleration Test After being treated at 80°C for 240 hours, it was re-evaluated.

(4) Fouling resistance evaluation method Fouling resistance evaluation method (dry method) % formula % A test piece (5 cm
x5cm)'1, the above standard synthetic cleansing powder 2: 500mg
, 10 hard balls 3 are placed in the container, and the container is fixed to a round-o-meter and rotated. After rotating at 40 rpm for 30 minutes, take out the test piece and rub it 20 times each in the vertical and horizontal directions with a nylon brush to remove the adhered dirt, or wipe it 3 to 5 times with a wet cloth and visually judge the degree of dirt. . The judgment criteria were as follows (initial stain).

After the above judgment, the sample was heat-treated at 80° C. for 240 hours, and then wiped with a wet cloth and the state of the stain was re-evaluated according to the judgment criteria (after staining).

Note that those with a judgment grade of 4 or higher are sufficiently durable for practical use.

Example 1 In a weft insertion raschel knitted fabric, high tenacity polyester fiber 1000 denier/192 filament was used as the warp insertion yarn, and high tenacity polyester fiber 10 was used as the weft insertion yarn.
00 denier/192 filament, high tenacity polyester fiber 50 denier/24 filament as leno thread, course density 13 threads/inch, weave density 1
It was composed of 2 pieces per inch. Polyvinyl chloride straight resin (manufactured by Kanegafuchi Kagaku Co., Ltd.; plasticizer, 65 parts of dioctyl phthalate, 0.0 parts of ultraviolet absorber) was applied to both sides of the coarse base fabric obtained.
2 parts, including other stabilizers, pigments, titanium dioxide, etc.), and one side of the topping is coated with polyvinylidene fluoride resin and methyl methacrylate resin at a ratio of 30:70 (
A marking sheet was obtained by mixing and thermally melting a film having a thickness of 25 μm to form an alloy at a weight ratio of 1) and laminating the film under heat.

The resulting sheet has good stain resistance and marking durability.

Example 2 In a warp-inserted raschel knitted fabric, high-strength polyester fibers of 500 denier/96 filaments were used as warp and weft-inserted yarns, high-strength polyester fibers of 50 denier/24 filaments were used as leno yarns, and the course density was 23/96 filaments.
The wafer was knitted at a low density of 22 wafers/inch. A sheet obtained by topping both sides of the coarse base fabric with the polyvinyl chloride resin of Example 1 was coated with polyvinylidene fluoride resin and methyl methacrylate resin in a ratio of 80:20.
(Weight ratio) Mixed and heat melted to form an alloy with a thickness of 10
A laminated film with a thickness of 30μ, which is made by integrating a film with a thickness of 30μ and a film with a thickness of 20μ obtained by mixing and melting both at a ratio of 20:80 (weight ratio>), was thermally laminated so that the 20μ film side was the inner layer. The light transmittance of the obtained sheet was 20%.A sheet with good stain resistance and marking capability was obtained.

Example 3 In warp insertion raschel knitted fabric, high tenacity polyester fibers of 500 denier/96 filaments were used as warp and weft insertion yarns, high tenacity polyester fibers of 50 denier/24 filaments were used as leno yarns, and the course density was 23/96 filaments.
The polyvinyl chloride resin of Example 1 was topped with the polyvinyl chloride resin of Example 1 on both sides of a coarse base fabric knitted with a small density of 22 wafers/inch. Polyvinylidene fluoride resin with a thickness of 4μ and a thickness of 6
A film made by laminating μ methyl methacrylate resin and 40 μ PVC resin in this order is attached to the above PVC resin.
Heat lamination was performed so that the vC resins adhered to each other.

The surface of the fluorine film of this sheet was gravure-coated with methyl methacrylate resin to an average thickness of 3 μm, and then thermally adhered to obtain a marking-enabled sheet with a stain-preventing effect.

Comparative Example 1 Trade name Lunashine ■■ (manufactured by Teijin ■) High strength polyester 500 used as warp and weft insertion yarn in warp and weft insertion raschel
Using polyester 100 denier/24 filament as leno thread,
A sheet made by laminating polyvinyl chloride on both sides of a base fabric knitted with a small wave density of 22 lines/inch and a coarse density of 23 lines/inch, and gravure coated the surface with methyl methacrylate); screen printing and thermal transfer marking are good, but stains The prevention effect is rather poor.

Comparative Example 2 A base fabric knitted with trade name First Sign (manufactured by Asahi Kasei ■, weft/warp insertion raschel) using polyester 1000 denier as the warp insertion yarn, polyester 50 denier as the leno yarn, and weft/warp yarn density of 12/inch. Laminate polyvinyl chloride on both sides, and cover the surface with polyvinyl fluoride resin film (Tetra Film).
Sheet adhered with DuPont ■ (12μ); Good stain prevention effect, but poor screen printing and thermal transfer marking properties.

Comparative Example 3 In the basic cloth warp insertion raschel of Example 1, polyester high strength filament 1000 denier/192 filament was used as the warp insertion yarn, polyester high strength filament 50 denier/24 filament was used as the leno yarn, and the course was The polyvinyl chloride straight resin of Example 1 was topping-processed on both sides of a coarse base fabric knitted with a density of 12 wires/inch and a small density of 11 wires/inch, and polyvinylidene fluoride resin and methyl methacrylate resin were applied to one side. Mix and heat melt at a ratio of 92:8 (weight ratio) to form an alloyed film with a thickness of 7 μm and both at a ratio of 20:8 (weight ratio).
Thickness 1 alloyed by mixing and melting at 80 (weight ratio)
A sheet made of a 25μ thick laminated film integrated with an 8μ film and thermally laminated with an 18μ film as the inner layer; great stain prevention effect but poor marking properties.

Comparative Example 4 The base fabric (warp and warp insertion raschel) of Example 2 was knitted using polyester high tenacity filament 500 denier/24 filament as the warp and warp insertion yarn, with a course density of 23 pieces/inch and a small way density of 22 pieces/inch. The sheet fluorine film is made by topping a coarse base fabric with the polyvinyl chloride resin of Example 1 on both sides, and thermally laminating a 35μ thick film with 4μ of polyvinylidene fluoride and 31μ of methyl methacrylate on the surface. (Using AT35Y): Good stain prevention effect, but poor screen printing and thermal transfer marking performance.

From the above results, Examples 1 to 3 have a marking effect and stain prevention effect, and Comparative Examples 1 to 5 fail.

[Brief explanation of drawings]

FIG. 1(a) shows a container for antifouling evaluation. Dao meter (b) is a lounge

Claims (6)

[Claims] (1) A resin-coated sheet formed by coating a base fabric with polyvinyl chloride resin and coating the resin with acrylic resin and fluororesin, characterized in that 9% or more of the acrylic resin is exposed. marking sheet. (2) The marking sheet according to claim (1), wherein 9 to 90% of the acrylic resin is exposed. (3) The marking sheet according to claim (1), wherein 20 to 50% of the acrylic resin is exposed. (4) The marking sheet according to any one of claims (1) to (3), wherein the acrylic resin and the fluororesin have a melting point or gelling temperature of 200°C or less. (5) Claim (1) that the light transmittance of the sheet is 5% or more.
The marking sheet according to any one of (4) to (4). (6) The surface layer of the sheet has a three-layer structure, with the outer layer mainly consisting of 9% or more acrylic resin and 91% or less fluororesin, the middle layer consisting of 70% or more fluororesin and 30% or less acrylic resin, and the inner layer (laminated to a polyvinyl chloride resin layer). Claim (1) wherein the layer) is made up of 30% or less fluororesin or 70% or more acrylic resin.
) to (5).