JP2003300289A - Stainproof waterproof sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stainproof waterproof sheet having high properties of preventing both a stain of dust and a stain of a streak of rain. <P>SOLUTION: A waterproof resin layer comprising a waterproof resin and a stainproof resin layer comprising a stainproof acrylic resin are formed sequentially on a base cloth comprising a fiber textile. A comb-shaped copolymer constituted of one polymer backbone chain segment per one molecule and a plurality of polymer branched chain segments connected like branches to the polymer backbone chain segment is used as the stainproof acrylic resin. The main constituent of the polymer backbone chain segment is the residual group of the copolymer of hydroxyalkyl(meth)acrylate and (meth)acrylic acid ester, while the main constituent of the polymer branched chain segment is the residual group of the copolymer of N-methylol(meth)acrylamide and the hydroxyalkyl(meth)acrylate. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a waterproof sheet having excellent antifouling properties. More specifically, the present invention relates to an antifouling waterproof sheet which is extremely useful for industrial material applications such as medium and large-sized tents, tent warehouses, eaves tents, truck hoods, and backlits for signboards.

[0002]

2. Description of the Related Art Conventionally, as a sheet for industrial materials such as medium and large tents, tent warehouses, eaves tents, hoods for trucks, back lits for signboards, for example, one side or both sides of a fibrous base cloth is synthesized. A laminate of waterproof resin layers made of rubber or synthetic resin is widely used. In particular, those using a polyvinyl chloride resin for forming the waterproof resin layer have a good balance of processability, economy, flameproofness, flexibility and the like, and are the most popular. Most of these tarpaulins are used outdoors, but as the period of use increases, smoke, soot, pollen, sap, etc. emitted from factories and automobiles, or feces of birds and insects, etc. It has been pointed out that the contaminants contaminate the surface of the sheet and impair the initial appearance.

In particular, a waterproof sheet having a waterproof resin layer formed of polyvinyl chloride resin contains a large amount of plasticizers, stabilizers, etc. in its composition, and therefore, even if the composition is thoroughly examined, it is used outdoors for a long time. If it is, the resin is gradually decomposed due to the influence of ultraviolet rays and rain (acid rain), and / or the plasticizer migrates to the surface, and the surface gradually becomes sticky, so that dust and dirt easily adhere to the sheet surface. It has the drawback of being easily soiled. In a membrane structure such as a tent warehouse constructed by using such a sheet, a part of the dirt attached to the ceiling sheet flows down to the side sheet due to rainfall, and the streak-like remarkable dirt on the side surface ( (Rain streaks stains). In applications such as medium- and large-sized tents and tent warehouses where the spread area is extremely large, it is difficult to wash even if the pollution becomes severe, and it is possible to continue using it without losing its aesthetic appearance or to use it for a short period of time. I have to switch to a new seat at home. Therefore, in the industry, there is a demand for the development of a sheet in which the surface of the sheet does not easily become dirty over a long period of time.

As a method for improving the antifouling property, for example,
It is common to coat the surface of polyvinyl chloride resin with acrylic resin dissolved in an organic solvent,
In this case, the plasticizer is dissolved in the organic solvent of the coating resin, or the liquid plasticizer or liquid stabilizer blended in the polyvinyl chloride resin migrates to the coating resin layer, so that the effect is not sufficient. Further, the method of coating the surface with a fluorine-containing resin instead of the acrylic resin (for example, Japanese Patent Laid-Open No. 60-260333) has the effect of suppressing the migration of the plasticizer as compared with the case of coating the acrylic resin. Although it has a characteristic that it is high and has a high barrier property against ultraviolet rays and rain, it does not have sufficient rain line stain prevention property. On the other hand, in the waterproof resin layer, a fluorine-containing resin (for example, JP-A-8-259638), a urethane resin (for example, JP-A-11-32376), an olefin resin such as ethylene-vinyl acetate resin ( For example, there are known sheets using a synthetic resin that can be molded without using a plasticizer, such as JP-A-2000-8276). The stain resistance is not sufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above problems of the prior art and intends to provide an antifouling waterproof sheet which is excellent in both the dirt stain resistance and rain streak stain resistance of the sheet. To do.

[0006]

Means for Solving the Problems The present inventor has diligently studied the above-mentioned problems, and as a result, a main chain segment composed of a polymer containing at least hydroxyalkyl (meth) acrylate and (meth) acrylic acid ester,
By forming an antifouling resin layer containing a comb-type copolymer composed of a branched chain segment composed of a polymer containing at least N-methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate, We found that the stain resistance and the rain streak stain resistance are improved,
The present invention has been completed based on this finding.

The antifouling waterproof sheet of the present invention is formed on a base cloth containing a fiber cloth and at least one surface of the base cloth,
And a sheet-shaped base material including a waterproof resin layer containing a waterproof resin, and an antifouling resin layer formed on the waterproof resin layer of the sheet-shaped base material and containing an antifouling acrylic resin. The antifouling acrylic resin of the antifouling resin layer comprises one polymer main chain segment per molecule, and a plurality of polymer branched chain segments branch-bonded to the polymer main chain segment. And a polymer main chain segment containing as a main component a copolymer residue of hydroxyalkyl (meth) acrylate and (meth) acrylic acid ester, It is characterized in that the combined branched chain segment contains a copolymer residue of N-methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate as its main component. In the antifouling waterproof sheet of the present invention, it is preferable that the antifouling resin layer further contains 10 to 200 parts by mass of colloidal silica with respect to 100 parts by mass of the comb-shaped acrylic copolymer. In the antifouling waterproof sheet of the present invention, the antifouling resin layer is selected from (1) ultrafine zinc oxide particles having an average particle size of 0.1 μm or less, and (2) a benzotriazole compound and a benzophenone compound. It is preferable to further include at least one selected from copolymers containing copolymerized units formed from at least one ultraviolet absorbing monomer. In the antifouling waterproof sheet of the present invention, the waterproof resin layer is a polyvinyl chloride resin, a polyolefin resin, a chlorinated polyolefin resin, an ethylene-vinyl acetate copolymer resin, an ethylene- (meth) acrylic acid ester. It is preferable to include at least one selected from a copolymer resin, a polyurethane resin, a polyester resin, an acrylic resin, and a fluorine-containing resin. In the antifouling waterproof sheet of the present invention, when the waterproof resin layer further contains an additive, an additive migration preventing layer is formed between the additive-containing waterproof resin layer and the antifouling resin layer. Is preferred. In the antifouling waterproof sheet of the present invention, when the backside waterproof resin layer formed on the backside of the base fabric further contains an additive, an additive migration prevention layer is formed on the additive-containing backside waterproof resin layer. Preferably. In the antifouling waterproof sheet of the present invention,
The additive migration prevention layer is a polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth)
Acrylic ester-based copolymer resin, fluorine-containing resin,
It is preferable to contain one or more kinds of synthetic resins selected from acrylic resins, urethane resins, and polyester resins. In the antifouling waterproof sheet of the present invention, the waterproof resin layer comprises (1) polyvinyl chloride resin and (2) molecular weight 4
00 or more phthalate ester plasticizer, molecular weight 420 or more aliphatic dibasic acid ester plasticizer, trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer,
Dipentaerythritol ester plasticizer, epoxy plasticizer, polyester plasticizer having a molecular weight of 600 or more, ester urethane polymer, ethylene-vinyl acetate-carbon monoxide terpolymer, and ethylene- (meth) acrylic acid It is preferable to include a plasticizer containing at least one selected from an ester-carbon monoxide terpolymer. In the antifouling waterproof sheet of the present invention, the sheet-shaped base material according to JIS
It is preferable that the weight loss by heating at 100 ° C. ± 2 ° C. for 6 hours according to K-6732-1981 is 1.0% or less. The antifouling waterproof sheet of the present invention may be wound up in a roll.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The fiber cloth used for the base fabric of the antifouling waterproof sheet of the present invention is a natural fiber such as cotton or hemp, an inorganic fiber such as a glass fiber, a carbon fiber or a metal fiber, and a recycled fiber. Semi-synthetic fibers such as viscose rayon and cupra, such as di- and triacetate fibers, and synthetic fibers such as polyamide fibers such as nylon 6 and nylon 66, aramid fibers such as Kevlar, polyethylene terephthalate and polyethylene naphthalate. Polyester fiber (saturated polyester fiber) such as and fatty acid polyester fiber such as polylactic acid fiber,
At least one selected from polyarylate fiber, aromatic polyether fiber, polyimide fiber, acrylic fiber, vinylon fiber, polyethylene fiber, polyolefin fiber such as polypropylene fiber and polyvinyl chloride fiber, etc.
You can choose from what consists of seeds.

Fiber material forming the fiber fabric in the base fabric
Are short fiber spun yarns, long fiber yarns, split yarns,
Any shape such as pull yarn may be used. Fiber for base cloth
The fabric structure is a woven fabric, a knitted fabric, a non-woven fabric, or a composite of these.
Either of them may be used. Exceptional to the weaving structure of fiber cloth
There is no limitation of, for example, at least each inter-thread gap
Yarns containing warp and weft yarns arranged in parallel with each other
Coarse knitted fabrics and non-coarse knitted fabrics
Includes knitted fabrics with virtually no gaps between the threads)
It Coarse fabric has a basis weight of 30 to 700 g / m² To be
And the through area ratio of the coarse knitted woven fabric is
10 to 95% of the total surface area of the object
preferable. When the fiber cloth is a non-coarse knitted fabric, the
There are no restrictions on the organization, basis weight, thickness, etc. of the
Knit fabrics such as plain weave, twill weave, circular knit, weft knit, and warp knit
Can be selected, and the basis weight is 50 to 1000 g /
m ² It is preferable to set the degree.

There is no particular limitation on the strength of the base cloth, but for use as a stretchable membrane material that is fixed under tension, it is 392 N / 3 cm (40 kgf / 3 cm).
It is preferable to have the above tensile strength. These base fabrics may be water-repellently treated in advance with a water repellent such as a fluorine compound or a silicone compound, and may be softened with a softening agent such as an amino-modified silicone compound. It may be

In the antifouling waterproof sheet of the present invention, the waterproof resin layer formed on at least one surface of the base cloth contains a waterproof resin, and the waterproof resin is a polyvinyl chloride resin or a polyolefin resin. Resin, chlorinated polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene-
(Meth) acrylic acid ester-based copolymer resin, ionomer-based resin (ethylene- (meth) acrylic acid-based copolymer salt, etc.), polyurethane-based resin, polyester-based resin (including aliphatic polyester-based resin), acrylic -Based resins, fluorine-containing resins, styrene-based copolymer resins (styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, and hydrogenated products thereof), polyamide-based resins, polyvinyl alcohol-based resins, It can be selected from ethylene-vinyl alcohol copolymer resins, silicone resins, and other synthetic resins (including thermoplastic elastomers). These waterproof synthetic resins may be used alone or as a mixture of two or more kinds. In particular, the waterproof resin layer is a polyvinyl chloride resin, a polyolefin resin, a chlorinated polyolefin resin, an ethylene-vinyl acetate copolymer resin,
It is preferable to contain at least one selected from ethylene- (meth) acrylic acid ester-based copolymer resins, polyurethane-based resins, polyester-based resins, acrylic-based resins, and fluorine-containing resins, and further polyvinyl chloride-based resins, Chlorinated polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid ester copolymer resin, polyurethane resin, polyester resin, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer It is more preferable to contain at least one selected from polymer resins. The waterproof resin layer containing these resins has good weldability of the sheet by high-frequency welding and can be suitably used for the antifouling waterproof sheet of the present invention.

In the antifouling waterproof sheet of the present invention, the polyvinyl chloride resin used for the waterproof resin layer is selected from vinyl chloride homopolymers and copolymers of vinyl chloride and other monomers. More than one species can be used. As a monomer copolymerizable with vinyl chloride, vinylidene chloride, vinyl acetate, ethylene, acrylonitrile,
(Meth) acrylic acid esters and the like can be used. It may also be a chlorinated polyvinyl chloride resin obtained by chlorinating a polyvinyl chloride resin.

In the antifouling waterproof sheet of the present invention, the polyolefin resin used for the waterproof resin layer is ethylene and at least one ethylenically unsaturated group selected from C _{3 to} C ₁₈ α-olefins. What was manufactured by the radical polymerization method, the ionic polymerization method, etc. using a monomer can be used. Various properties of these polyolefin resins can be obtained depending on the catalyst used during polymerization. For example, those manufactured using a catalyst such as a Ziegler catalyst or a metallocene catalyst can be used. It is preferable to use a polyethylene resin and a polypropylene resin. In addition, EPR is added to these resins.
It is also possible to use a polyolefin elastomer obtained by melt-kneading EPDM or dynamically crosslinking it.

In the antifouling waterproof sheet of the present invention, the chlorinated polyolefin resin used for the waterproof resin layer is a low chlorinated polyethylene resin, a high chlorinated polyethylene resin, a low chlorinated polypropylene, or a high chlorinated polypropylene. A system resin can be used. These can be obtained by, for example, making polyethylene or polypropylene powder into an aqueous suspension and blowing chlorine gas into the system at a temperature near the crystal melting point of the raw material resin.

In the antifouling waterproof sheet of the present invention, the ethylene-vinyl acetate copolymer resin used for the waterproof resin layer has a relatively high content of vinyl acetate component produced by the radical polymerization method of the high pressure method. Low copolymer resin,
And a copolymer resin having a relatively high vinyl acetate component content produced by a low pressure solution polymerization method may be used.
The content of the vinyl acetate component in the ethylene-vinyl acetate copolymer resin is preferably 10% by mass to 95% by mass. Those having a high vinyl acetate component content are preferable because of their high weldability during high-frequency welding. For these ethylene-vinyl acetate copolymer resins, those having a vinyl acetate component content within the above range are used alone or as a mixture of two or more copolymers having different vinyl acetate component contents. May be.

In the antifouling waterproof sheet of the present invention, the ethylene- (meth) acrylic acid ester-based copolymer resin used for the waterproof resin layer may be a copolymer resin produced by a radical polymerization method, It can be obtained by polymerizing ethylene monomer with at least one acrylic comonomer selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Also, with these, acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid and maleic acid, acid anhydrides such as maleic anhydride, epoxy group-containing monomers such as glycidyl methacrylate and other ethylenic comonomers may be used in combination.

In the antifouling waterproof sheet of the present invention, as the polyurethane resin used for the waterproof resin layer, a resin obtained by reacting a polymer polyol, polyisocyanate, and optionally a chain extender is used. it can. As the polymer polyol used for such urethane-based resin, it is possible to use a polyester-based polyol having hydroxyl groups at both ends of a molecular chain, a polyether-based polyol, a polycarbonate-based polyol, a polyesteramide polyol, or an acrylate-based polyol. it can. 2,4 as polyisocyanate
-Use of aromatic polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, aliphatic polyisocyanates such as tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate, alicyclic polyisocyanates such as hydrogenated xylylene diisocyanate and isophorone diisocyanate You can As the chain extender, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
Hexanediol, low molecular weight polyols such as diethylene glycol, ethylenediamine, propylenediamine,
Butylenediamine, aliphatic polyamines such as hexamethylenediamine, piperazine, 1,4-diaminopiperazine, alicyclic polyamines such as 1,3-cyclohexylenediamine, diphenylmethanediamine, tolylenediamine, aromatic polyamines such as phenylenediamine, Alkanolamines such as ethanolamine and propanolamine can be used. In particular, a urethane resin using an aliphatic polyisocyanate or an alicyclic polyisocyanate as a polyisocyanate component is preferable because it does not yellow due to exposure to ultraviolet rays and has good weather resistance.

In the antifouling waterproof sheet of the present invention, as the polyester resin preferably used for the waterproof resin layer, dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative are esterified and polycondensed. The resin obtained by the above can be used. Further, it may be a cyclic ester such as β-propiolactone, β-butyrolactone, δ-valerolactone, ε-caprolactone or an aliphatic polyester resin obtained by ring-opening polymerization of lactide. Examples of the dicarboxylic acid for producing a polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid and ester-forming derivatives thereof, fats such as adipic acid, succinic acid and sebacic acid. Use of at least one member selected from hydroxycarboxylic acids such as group-dicarboxylic acids and ester-forming derivatives thereof, p-hydroxybenzoic acid, p- (β-hydroxyethoxy) benzoic acid, and ester-forming derivatives thereof. You can On the other hand, the diol component for producing the polyester resin may be any of aliphatic, aromatic and alicyclic compounds, and examples thereof include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and dipropylene glycol. , 1,6-
Hexanediol, 1,4-cyclohexanediol,
One or more selected from xylylene glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, poly (tetramethylene oxide) glycol and the like can be used.

In the antifouling waterproof sheet of the present invention, the acrylic resin used for the waterproof resin layer is a polymer or copolymer containing acrylic acid or methacrylic acid C _{1 to} C ₄ alcohol ester as a main constituent monomer. It is preferable to use a resin whose main component is coalescence. As a main constituent monomer of such an acrylic resin, specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate can be used, and methyl acrylate is particularly preferable. And methyl methacrylate are preferred. Examples of the monomer copolymerized with these main constituent monomers include acrylic acid or methacrylic acid, and C _{1 to} C of acrylic acid or methacrylic acid.
₁₂ alcohol ester, 2-hydroxyethyl methacrylate, glycidyl methacrylate, N-methylol acrylamide, N, N-dimethylaminoethyl methacrylate, methyl vinyl ether, vinyl ethoxysilane, α-methacryloxypropyltrimethoxysilane,
Vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, acrylonitrile,
Mention may be made of ethylenically unsaturated monomers such as methacrylonitrile and butadiene. These copolymers are not limited to random copolymers and may be graft copolymers. In addition, an acrylic resin containing an ethyleneimine residue, an alkylenediamine residue, or the like can also be used.

In the antifouling waterproof sheet of the present invention, the waterproof resin layer has a plasticizer, a softening agent, a stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a filler, a flame retardant,
If necessary, one or more additives selected from colorants, algae-proofing agents, antifungal agents, antibacterial agents, antistatic agents, curing agents and the like can be mixed and used. As these additives, additives known in the art can be used without limitation. Examples of plasticizers include phthalic acid ester-based, adipic acid ester-based, fumaric acid ester-based, maleic acid ester-based, azelaic acid ester-based, sebacic acid ester-based, citric acid ester-based, phosphoric acid ester-based, and polyester-based plasticizers. An agent can be illustrated. Examples of the softening agent include paraffin-based, petroleum distillate-based, aromatic hydrocarbon-based and vegetable oil-based softening agents. Examples of the stabilizer include organic tin-based, phosphite-based, and metal soap-based stabilizers. Examples of the antioxidant include hindered phenol-based, amine-based, phosphite-based, and organic sulfur-based antioxidants. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, and salicylic acid-based ultraviolet absorbers. Examples of the light stabilizer include hindered amine-based and benzoate-based light stabilizers. Examples of the lubricant include paraffin-based, fatty acid-based, ester-based, amide-based, phosphate ester-based, and metal soap-based lubricants.

Examples of fillers include inorganic fillers such as calcium carbonate, calcium silicate, barium sulfate, zinc oxide, alumina, silica, kaolin clay, talc, diatomaceous earth, mica, glass beads, styrene beads, acrylic beads, and cellulose beads. Examples include organic fillers such as nylon beads, urea beads, and collagen powder. As the flame retardant, red phosphorus-based, phosphate ester-based, halogen-containing phosphate ester-based, condensed phosphate ester-based, polyphosphate-based, chlorine-based, bromine-based, triazine derivative-based,
Examples thereof include organic flame retardants such as hindered amine type and silicone type resins, and inorganic type flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony type, zirconium type and zinc borate. As the colorant, titanium oxide type, iron oxide type, chromic acid type, cadmium type, complex oxide type, pearl, mica, aluminum, inorganic colorants such as carbon black, azo type, phthalocyanine type, quinacridone type,
Examples include organic colorants such as isocindolinone-based, perylene-based, perinone-based, anthraquinone-based, quinophthalone-based, and pyrrole-based colorants. Examples of the anti-algal agent include pyrithione-based anti-algal agents. As the fungicide, organic nitrogen type, organic nitrogen sulfur type, halogenated organic nitrogen type, organic nitrogen sulfur halogen type, halogenated organic acid ester type, benzimidazole type, pyrithione type, quaternary ammonium type antifungal agent Can be illustrated. Examples of the antibacterial agent include organic acid metal salt-based, silver-based, zinc-based, and copper-based antibacterial agents. Examples of the antistatic agent include surfactants, cationic polymer-based, anionic polymer-based, tin oxide antimony oxide-based antistatic agents and the like. Examples of the curing agent include isocyanate type, oxazoline type, carbodiimide type, aziridine type, melamine type, epoxy type and coupling agents.

In the antifouling waterproof sheet of the present invention, when a polyvinyl chloride resin is used for the waterproof resin layer, a phthalate ester plasticizer having a molecular weight of 400 or more and a molecular weight of 42 are used.
0 or more aliphatic dibasic acid ester plasticizer, trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer, epoxy plasticizer, dipentaerythritol ester plasticizer, molecular weight 600 or more polyester plasticizer , At least one liquid plasticizer selected from, and ester-based urethane polymers, ethylene-vinyl acetate-carbon monoxide terpolymer, ethylene- (meth) acrylic acid ester-carbon monoxide ternary copolymer It is preferable to use at least one polymer plasticizer selected from coalesce and at least one plasticizer selected as a main plasticizer. These plasticizers have extremely high volatility as compared with the conventional plasticizers for polyvinyl chloride resins such as dibutyl phthalate, di2-ethylhexyl phthalate, di-n-octyl phthalate and dioctyl adipate. It is suitable because it is very low and migration is low. In particular, polyester plasticizer,
And it is preferable to use the above-mentioned polymer plasticizers.

In the polyvinyl chloride resin for the waterproof resin layer, examples of the phthalate ester plasticizer having a molecular weight of 400 or more include diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, and butylbenzyl phthalate. Can be used. As the aliphatic dichlorate ester plasticizer having a molecular weight of 420 or more, diisodecyl adipate, dibutoxyethyl adipate, di-2-ethylhexyl sebacate, di-2-ethylhexyl dodecanoate, or the like can be used. Since the aliphatic dibasic acid ester plasticizer is slightly more volatile than the phthalic acid ester plasticizer having an equivalent molecular weight, it is preferable to select one having a higher molecular weight. As the trimellitic acid ester-based plasticizer and the pyromellitic acid ester-based plasticizer, those obtained by condensation reaction of trimellitic acid and monohydric alcohol and pyromellitic acid and monohydric alcohol can be used. As the trimellitic acid ester plasticizer, tris-2-ethylhexyl trimellitate, trisisodecyl trimellitate and the like can be used, and as the pyromellitic acid ester plasticizer, tetra-2-ethylhexyl pyromellitic acid and the like can be used. As the epoxy plasticizer, epoxidized soybean oil, epoxidized linseed oil and the like can be used. Examples of polyester plasticizers include dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and phthalic acid, ethylene glycol, 1,2-butanediol,
It is possible to use a polyester obtained by optionally polycondensing a diol such as 1,6-hexanediol. The molecular weight of the polyester plasticizer is 60
It is preferably 0 or more, more preferably 1000
As described above, it is more preferably 1500 to 4000. When the molecular weight is too small, volatility becomes high and migration becomes high, which is not preferable. On the other hand, if the molecular weight is too large, the processability may be deteriorated, for example, the melt viscosity when kneaded and blended with the polyvinyl chloride resin becomes high.

As the ester urethane polymer, a resin obtained by reacting a polyester polymer polyol, polyisocyanate, and optionally a chain extender can be used. Examples of urethane-based polymers include ester-based urethane polymers, ether-based urethane polymers, carbonate-based urethane polymers, etc., but ester-based urethane polymers have high plasticization efficiency for polyvinyl chloride-based resins. , Most preferred. In particular, as polyisocyanates, aliphatic diisocyanates such as tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate, isophorone diisocyanate,
The ester-based urethane polymer obtained by using an alicyclic diisocyanate such as hydrogenated xylylene diisocyanate is not only yellowed by exposure to ultraviolet rays, but also more polyvinyl chloride than when an aromatic diisocyanate is used. High plasticization efficiency of resin
It is suitable. Ester-based urethane polymer, ethylene-vinyl acetate-carbon monoxide terpolymer, ethylene-
The polymer plasticizer selected from the (meth) acrylic acid ester-carbon monoxide terpolymer has a molecular weight significantly higher than that of conventional plasticizers, and thus is non-volatile and non-extractable. , The molded product shows excellent durability.

When an acrylic resin is used for the waterproof resin layer in the antifouling waterproof sheet of the present invention, plasticizers that can be suitably added to the acrylic resin for the purpose of imparting flexibility include dibutyl phthalate and phthalic acid. Examples of the plasticizer include dioctyl, butylbenzyl phthalate, myristylbenzyl phthalate, tributyl acetylcitrate, diphenyldecyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate. Since these plasticizers have high polarity and good compatibility with the acrylic resin, it is difficult for the plasticizer to migrate to the surface.

In the antifouling waterproof sheet of the present invention, when the waterproof resin layer of the sheet-shaped substrate contains an additive, the weight loss on heating of the sheet-shaped substrate measured according to JIS K-6732-1981 is 1.0. % Or less is preferable. When the weight loss on heating of the sheet-shaped substrate exceeds 1.0%, good antifouling property may not be maintained for a long period of time. It is not clear why the antifouling property decreases when the heating loss exceeds 1.0%, but when the sheet is used outdoors, the temperature of the waterproof resin layer rises due to the effect of solar radiation during the day. It is presumed that the additive contained in the inside gradually volatilizes, which reduces the antifouling property of the antifouling layer. Therefore, it is preferable to use low volatility plasticizers and softeners that are mixed with the synthetic resin, and in the case where high volatility agents must be used, the addition amount should be kept small. The heating loss is preferably 1.0% or less. The loss on heating is more preferably 0.50% or less.

In the antifouling waterproof sheet of the present invention, the thickness of the waterproof resin layer can be appropriately set according to the basis weight of the base cloth and the intended use. Thick enough to provide dynamic strength, for example,
It is preferable to adjust it to 0.01 to 2.0 mm, and 0.0
It is more preferable to adjust to 5 to 1.5 mm. Further, the waterproof resin layer may be composed of one or more layers made of the same resin or two or more layers made of different resins on the base cloth, and the waterproof resin layers made of different resins are provided on the front and back of the base cloth. You may form.

In the antifouling waterproof sheet of the present invention, the waterproof resin layer is formed of a film, a solution, an emulsion, a paste sol or the like containing the above synthetic resin or the above synthetic resin and a plasticizer and / or a softening agent. It can be formed on the base fabric by a method such as topping, calendering, coating, and dipping.

In the antifouling waterproof sheet of the present invention, an antifouling resin layer containing an antifouling acrylic resin is formed on the waterproof resin layer of the sheet-shaped substrate. The acrylic resin comprises a comb-type copolymer composed of one polymer main chain segment per molecule and a plurality of polymer branch chain segments branch-bonded to the polymer main chain segment. The polymer main chain segment contains, as its main component, a copolymer residue of hydroxyalkyl (meth) acrylate and (meth) acrylic acid ester, and the polymer branch chain segment has The main component contains a copolymer residue of N-methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate.

In the antifouling waterproof sheet of the present invention, the main chain segment of the antifouling acrylic resin is mainly composed of a copolymer residue of hydroxyalkyl (meth) acrylate and (meth) acrylic acid ester. Contains. As hydroxyalkyl (meth) acrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-
One or more selected from hydroxybutyl methacrylate can be used. Since hydroxyalkyl (meth) acrylate has a hydroxyl group in the side chain, the polymer containing it exhibits hydrophilicity and contributes to the antifouling property of the antifouling layer and the rain streak antifouling property. Examples of the (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
One or more selected from butyl acrylate and butyl methacrylate can be used. These (meta)
By copolymerizing an acrylic ester with hydroxyalkyl (meth) acrylate, the water resistance and weather resistance of the resulting antifouling acrylic resin can be improved. It is particularly preferable to use methyl methacrylate.

In the antifouling waterproof sheet of the present invention, the hydroxyalkyl (meth) acrylate and (meth) acrylic acid ester used in the main chain segment of the antifouling acrylic resin are based on the total amount of monomers for the main chain segment. , 40% by mass or more of hydroxyalkyl (meth) acrylate and 5% by mass or more of (meth) acrylic acid ester, and the total amount thereof is preferably 70% by mass or more. When the content of hydroxyalkyl (meth) acrylate is less than 30% by mass, the hydrophilicity of the resulting antifouling acrylic resin may be insufficient. On the other hand, if the content of the (meth) acrylic acid ester is less than 5% by mass, the weather resistance of the resulting antifouling acrylic resin may be insufficient.

In the antifouling waterproof sheet of the present invention, the copolymer forming the main chain segment of the antifouling acrylic resin contains less than 30% by mass (the total of the main component monomers) in addition to the main component monomers. A monomer different from the hydroxyalkyl (meth) acrylate and the (meth) acrylic acid ester may be copolymerized within a range of less than 30% by mass with respect to the mass. As the different monomer copolymerizable with the hydroxyalkyl (meth) acrylate and the (meth) acrylic acid ester, for example, an ethylenically unsaturated monomer can be used. Examples of the ethylenically unsaturated monomer that can be used for the main chain polymer segment include, for example, ethylene, propylene, butylene,
Α-Olefins such as isobutylene, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid and salts thereof, acid anhydrides such as maleic anhydride and itaconic anhydride, acrylic acid or methacrylic acid C ₅ -C ₁₂ alcohol esters of the acid, hydroxypropyl vinyl ether, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, epoxy groups, such as hydroxyalkyl (meth) hydroxyl group-containing monomers other than acrylates, glycidyl methacrylate, such as methyl triglycol methacrylate Contained monomer, acrylamide, maleic acid amide, N- (2-hydroxyethyl) acrylamide, methacrylamide, N- (2-hydroxyethyl)
Amide group-containing monomers such as methacrylamide, butoxymethylolacrylamide, butoxymethylolmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, Amino group-containing monomers such as N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate and vinylpyridine, vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, phenyl Vinyl ethers such as vinyl ether, cyano group-containing monomers such as acrylonitrile, methacrylonitrile and fumaronitrile, methyl vinyl chloride Ketone, ethyl vinyl ketone,
Vinyl ketones such as propyl vinyl ketone and phenyl vinyl ketone, vinyl amides such as N-vinyl acetamide, vinyl chloride, vinylidene chloride, vinyl fluoride,
Halogen-containing α, β-unsaturated monomers such as vinylidene fluoride, fluorine-modified monomers such as trifluoroethyl methacrylate and hexafluoropropylene methacrylate, and styrenes such as styrene, methylstyrene and chloromethylstyrene can be used.

In the antifouling waterproof sheet of the present invention, the main component monomers of the copolymer forming the side chain segment of the antifouling acrylic resin are N-methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate. . As N-methylol (meth) acrylamide,
N-methylol acrylamide and N-methylol methacrylamide can be used. In the antifouling waterproof sheet of the present invention, N-methylol (meth) acrylamide used in the branched polymer segment of the antifouling acrylic resin is contained in an amount of 10% by mass or more based on the total amount of the monomers for the branched polymer segment. Is preferable, and it is more preferable that the content is 20% by mass or more. N-methylol (meth) acrylamide, in addition to having hydrophilicity itself, due to the high reactivity of the methylol group, by cross-linking with each other, or with a hydroxyl group, an epoxy group, The water resistance of the antifouling acrylic resin of the present invention is improved. As hydroxyalkyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
One or more selected from 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like can be used. In the antifouling waterproof sheet of the present invention, the hydroxyalkyl (meth) acrylate used in the branched polymer segment of the antifouling acrylic resin contains 10% by mass or more with respect to the total amount of the monomers for the branched polymer segment. It is preferable to contain 20 mass% or more, and it is more preferable to contain 20 mass% or more. Since hydroxyalkyl (meth) acrylate has a hydroxyl group in the side chain, the polymer containing it exhibits hydrophilicity and contributes to the antifouling property of the antifouling layer and the rain streak antifouling property. Further, the total content of the main component monomer, N-methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate of the copolymer for branch chain segment is preferably 70% by mass or more.

Further, in the antifouling waterproof sheet of the present invention, in addition to the above-mentioned main component monomer, less than 30% by mass (of the main component monomer) is used to form the polymer forming the branch chain segment of the antifouling acrylic resin. In the range of less than 30% by mass with respect to the total amount), a monomer different from that may be copolymerized. As the different monomer copolymerizable with N-methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate, for example, an ethylenically unsaturated monomer can be used. Examples of the ethylenically unsaturated monomer that can be used as the monomer for the branched polymer segment include, for example, α-olefins such as ethylene, propylene, butylene, and isobutylene, α, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid. , Β-unsaturated carboxylic acids and salts thereof, acid anhydrides such as maleic anhydride and itaconic anhydride, esters of C ₁ -C ₁₂ alcohols of acrylic acid or methacrylic acid, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl vinyl ether, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, methyltriglycol methacrylate and other hydroxyl group-containing monomers, glycidyl methacrylate and other epoxy group-containing monomers, acrylamide, maleic acid amide , N-
Amide group-containing monomers such as (2-hydroxyethyl) acrylamide, methacrylamide, N- (2-hydroxyethyl) methacrylamide, butoxymethylolacrylamide, butoxymethylolmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide , N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate,
N, N-diethylaminoethyl acrylate, N, N-
Amino group-containing monomers such as diethylaminoethyl methacrylate and vinyl pyridine, vinyl acetates such as vinyl acetate, vinyl propionate and vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether and phenyl vinyl ether, acrylonitrile, methacrylonitrile,
Cyano group-containing monomers such as fumaronitrile, vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone, N-
Vinylamides such as vinylacetamide, halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride, fluorine-modified monomers such as trifluoroethyl methacrylate and hexafluoropropylene methacrylate, styrene, methyl Styrenes such as styrene and chloromethylstyrene can be used.

In the antifouling waterproof sheet of the present invention, the method for producing the antifouling acrylic resin is not particularly limited, but the method obtained by the macromonomer method is preferable. The macromonomer method is a method of preliminarily synthesizing a polymer having a polymerizable functional group such as a vinyl group at one end and polymerizing this with an ordinary ethylenically unsaturated monomer to obtain a comb-type copolymer. As a method for obtaining a macromonomer having a vinyl group at one end, for example, a method of performing anionic living polymerization of methyl methacrylate, etc., and then reacting with a halogen-containing vinyl compound, of the ethylenically unsaturated monomer in the presence of mercaptoacetic acid There is a method of performing radical polymerization and then reacting the obtained polymer or oligomer with an epoxy group-containing monomer such as glycidyl methacrylate. The antifouling acrylic resin macromonomer of the present invention can be obtained, for example, by the method described in JP-B-6-80088.

In the antifouling waterproof sheet of the present invention, the molecular weight of the antifouling acrylic resin used in the antifouling resin layer is 5
It is preferably from 10,000 to 1,000,000, more preferably from 100,000 to 500,000. When the molecular weight is less than 50,000, the resulting antifouling resin layer may not have sufficient mechanical strength, and when it exceeds 1,000,000, the solution viscosity becomes high and the coating property becomes poor. May be insufficient. still,
The molecular weight of the branched polymer segment is such that when a macromonomer is used for the branch chain, the molecular weight of the macromonomer is 1.00.
It is preferably from 0 to 100,000, and 3,000
More preferably, it is 50,000. If the molecular weight is 1,000 or less, the resulting comb-type copolymer may have insufficient properties (particularly hydrophilicity), and it is 10 or less.
If it exceeds 50,000, the reactivity of the macromonomer may be insufficient.

In the antifouling waterproof sheet of the present invention, the antifouling resin layer may contain a synthetic resin different from the antifouling acrylic resin. As the heterogeneous synthetic resin that can be mixed with the antifouling acrylic resin, an acrylic resin, a fluorine resin, a urethane resin, a polyester resin, or the like can be used. Among these, the acrylic resin and the fluorine resin are used. It is preferable. The amount of these different synthetic resins added to the antifouling layer is preferably 50 parts by mass or less based on 100 parts by mass of the antifouling acrylic resin.
If it is added in an amount of more than 50 parts by mass, the hydrophilicity of the obtained antifouling resin layer may be insufficient, and thus the antifouling property may be insufficient.

In the antifouling waterproof sheet of the present invention, in the antifouling resin layer, an ultraviolet absorber, an antioxidant, a light stabilizer,
If necessary, one or more additives selected from an algae-proofing agent, a fungicide, an antibacterial agent, a flame retardant, a filler, a coloring agent, a curing agent and the like can be mixed and used. As an ultraviolet absorber,
Examples include benzotriazole-based, benzophenone-based, and cyanoacrylate-based ultraviolet absorbers. Examples of the antioxidant include hindered phenol-based, amine-based, phosphite-based, and organic sulfur-based antioxidants. Examples of the light stabilizer include hindered amine-based and benzoate-based light stabilizers. As an algae repellent,
Examples of the anti-algal agent include pyrithione. Antifungal agents include organic nitrogen-based, organic nitrogen-sulfur-based, halogenated organic nitrogen-based, organic nitrogen-sulfur-halogen-based, halogenated organic acid ester-based, benzimidazole-based, pyrithione-based, quaternary ammonium-based, etc. An agent can be illustrated. Examples of the antibacterial agent include organic acid metal salt-based, silver-based, zinc-based, and copper-based antibacterial agents. Examples of flame retardants include red phosphorus-based, phosphate-based, halogen-containing phosphate-based, condensed phosphate-based, polyphosphate-based, chlorine-based, bromine-based, triazine-derivative-based, hindered amine-based, and silicone-based resins. Examples thereof include organic flame retardants, inorganic hydroxides such as aluminum hydroxide, magnesium hydroxide, antimony, zirconium and zinc borate. As the filler, calcium carbonate, calcium silicate, barium sulfate, zinc oxide,
Alumina, silica, kaolin clay, talc, diatomaceous earth,
Examples thereof include inorganic fillers such as mica and glass beads, and organic fillers such as styrene beads, acrylic beads, chitosan beads, cellulose beads, nylon beads, urea beads and collagen powder. As the colorant, titanium oxide-based, iron oxide-based, chromic acid-based, cadmium-based, composite oxide-based, pearl, mica, aluminum, inorganic colorants such as carbon black, azo-based, phthalocyanine-based, quinacridone-based, iso Examples of organic colorants include syndolinone-based, perylene-based, perinone-based, anthraquinone-based, quinophthalone-based, and pyrrole-based colorants. Examples of the curing agent include isocyanate type, oxazoline type, carbodiimide type, aziridine type, melamine type, epoxy type and coupling agents.

In the antifouling waterproof sheet of the present invention, colloidal silica is preferably added to the antifouling resin layer. By adding colloidal silica, the antifouling property of the antifouling resin layer can be further improved. As the colloidal silica, those obtained by a method using an ion exchange method with an aqueous sodium silicate solution as a raw material can be used. Chemical industry, etc., and the commercially available products under the trade name can be used. Further, it may be colloidal silica obtained by hydrolyzing an organosilicate such as ethyl silicate in the presence of an alkali. As the organosilicate, for example, those commercially available under the trade name of MKC silicate (Mitsubishi Chemical) can be used.

In the antifouling waterproof sheet of the present invention, the antifouling resin layer comprises (1) ultrafine zinc oxide particles having an average particle size of 0.1 μm or less, and (2) a benzotriazole compound and / or a benzophenone compound. At least one selected from the copolymers containing a copolymerized unit formed from at least one ultraviolet absorbing monomer selected from the above may be contained. These compounds have high ultraviolet absorption, and by adding them, ultraviolet deterioration of the antifouling acrylic resin and waterproof resin layer used for the antifouling resin layer can be suppressed. These compounds do not migrate even if added to the antifouling resin layer, and therefore do not reduce the antifouling property of the antifouling resin layer. Even when the antifouling resin layer is transparent, the change in transparency of the antifouling resin layer can be minimized.

The zinc oxide ultrafine particles for the antifouling resin layer may be surface-treated with a silicone resin or the like. Such zinc oxide ultrafine particles include, for example, Z
Commercially available products such as nO-100, ZnO-200 (above, manufactured by Sumitomo Osaka Cement), and TZO (manufactured by Elementis Japan) can be used. The amount of the zinc oxide ultrafine particles added to the antifouling layer is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the antifouling acrylic resin contained in the antifouling layer. It is more preferably 0.1 to 5 parts by mass. When the amount is 0.05 parts by mass or less, the effect of suppressing the deterioration of the antifouling layer by ultraviolet rays is not sufficient, and the addition of more than 10 parts by mass does not change the effect and increases the cost.

The copolymer obtained by copolymerizing a benzotriazole compound and / or a benzophenone compound is, for example, a benzotriazole compound having a methacryloyl group and / or a benzophenone compound, methyl methacrylate and / or styrene. It can be obtained by radical copolymerization with the above. Alternatively,
A benzotriazole-based compound or a benzophenone-based compound having a hydroxyethyl group, an acrylic polymer,
It can be obtained by graft copolymerization with a polymer such as a urethane polymer or a polyester polymer. Specifically, as an acrylic copolymer having a benzotriazole-based compound in the side chain, Sunlife US (manufactured by Nichika Chemical Co., Ltd.), ULS-933LP (manufactured by Yatsusha Yushi Kogyo Co., Ltd.), PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) As an acrylic copolymer having a benzophenone-based compound in the side chain, UCI-635L (manufactured by Yatasha Yushi Kogyo Co., Ltd.), and a styrene-based copolymer having a benzotriazole-based compound, PUVA-30S (Otsuka Chemical), etc. Commercially available products of can be used. These can be arbitrarily selected in consideration of compatibility with the resin used for the antifouling resin layer. The addition amount of these copolymers in the antifouling resin layer is 5 to 5 with respect to 100 parts by mass of the antifouling acrylic resin in the antifouling layer.
It is preferably 0 part by mass. If it is less than 5 parts by mass, the effect of suppressing ultraviolet deterioration of the antifouling layer may not be sufficient, and if it is added in excess of 50 parts by mass, the hydrophilicity of the waterproof layer becomes insufficient and the antifouling property becomes insufficient. Sometimes.

In the antifouling waterproof sheet of the present invention, an adhesive layer may be formed between the antifouling resin layer and the waterproof resin layer. By forming the adhesive layer, the adhesion of the antifouling resin layer to the waterproof resin layer can be improved. As the resin that can be used for the adhesive layer, polyvinyl chloride resin, acrylic resin, polyurethane resin, polyethylene resin, epoxy resin, melamine resin, polypropylene resin, polyamide resin, polyester resin, ethylene -At least one selected from synthetic resins such as vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, polyvinyl alcohol resin, polyvinyl butyral resin, silicone resin, fluorine-containing resin and fluorine-modified resin Synthetic resins can be used. Further, the antifouling resin layer may be formed via a natural rubber-based, synthetic rubber-based, recycled rubber-based, acrylic-based, silicone-based, or other pressure-sensitive adhesive. The adhesive layer has an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, a filler, a coloring agent,
If desired, one or more additives selected from a curing agent and the like can be mixed and used.

In the antifouling waterproof sheet of the present invention, as a method for forming an adhesive layer, a film, a solution, an emulsion or the like containing the above-mentioned synthetic resin for the adhesive layer, an adhesive or the like is used, and a known method, for example, It can be formed on the sheet by a method such as topping, laminating and coating. The thickness of the adhesive layer is not particularly limited, but is preferably 0.3 to 200 μm, for example. If the thickness of the adhesive layer is less than 0.3 μm, a special processing machine is required, which may cause manufacturing difficulties. When the thickness is more than 200 μm, there may be a problem such that the texture of the sheet becomes hard.

In the antifouling waterproof sheet of the present invention, when the waterproof resin layer of the sheet-shaped substrate contains an additive, the additive in the waterproof resin layer is added between the waterproof resin layer and the antifouling resin layer. An additive migration prevention layer for preventing migration to the dirty resin layer may be formed. As the synthetic resin used in the additive migration prevention layer, polyvinyl chloride resin, polyolefin resin, ionomer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, polyvinyl alcohol resin, Polyvinyl butyral resin, cellulose ester resin, cellulose ether, polyurethane resin (including aliphatic polyester resin), polyester resin, acrylic resin,
At least one kind of synthetic resin selected from polycarbonate-based resin, polyamide-based resin, epoxy-based resin, melamine-based resin, silicone-based resin, fluorine-containing resin and the like can be used. In particular, it is preferable to use one or more selected from fluorine-containing resins, acrylic resins, polyurethane resins, and polyester resins. In the additive migration prevention layer, one or more kinds of additives selected from an antifouling layer, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, a filler, a coloring agent, a curing agent, etc. may be added as required. It can be mixed and used.

In the antifouling waterproof sheet of the present invention, when the waterproof resin layer containing an additive is formed on both surfaces of the base fabric and the antifouling resin layer is formed only on one surface (surface) of the base resin, the other It is preferable to form an additive migration preventing layer on the surface (back surface). By forming the additive migration prevention layer, in a state in which the sheet is wound in a roll shape and stored, migration components such as additives contained in the waterproof resin layer on the back surface of the antifouling resin layer on the front surface It is possible to prevent the adhesion. As in the case of the antifouling waterproof sheet of the present invention, in the case of having a hydrophilized antifouling resin layer, the antifouling property reduction caused by the attachment of the additive to the antifouling resin layer is not hydrophilized. Since it is more remarkable, by providing the additive migration prevention layer on the back surface, the original antifouling property of the antifouling resin layer can be exhibited when the sheet is actually used. When the sheet of the present invention is used as a roll-up body, the winding method is not particularly limited, but for example, when rolling up a waterproof sheet having an antifouling resin layer formed on only one side, an antifouling layer is used. It is preferable to wind up inside. By doing this, the back surface of the sheet is exposed at the outermost periphery of the roll-shaped roll, and it is possible to prevent unburned stains and scratches on the antifouling resin layer that accompany the work of moving the roll-shaped roll. .

In the antifouling waterproof sheet of the present invention, as a method for forming the additive migration preventing layer, a film, solution, emulsion or the like containing the above-mentioned polymer for the additive migration preventing layer is used, and a known method is used. For example, it can be formed on the sheet by a method such as topping, laminating and coating. The thickness of the additive migration prevention layer is more preferably 0.3 to 200 μm. More preferably, it is 1 to 100 μm. 0.3
If it is less than μm, the effect of preventing the migration of the additive from the waterproof resin layer is low, and if it exceeds 200 μm, the effect is not changed, and there is an adverse effect such as a hard texture, which is not preferable.

[0048]

The present invention will be further described by the following examples.

[Evaluation Method] The performance of the antifouling sheet of the present invention was evaluated by the test method shown below. 1. Evaluation of Antifouling Property Regarding the test sheet, the sheet was arranged facing south, with an inclination angle of 30 degrees and vertically, and this was subjected to an outdoor exposure test to evaluate the antifouling property of the sheet and the state of occurrence of rain streak contamination. (1) Difference in lightness (ΔL) on the surface of the sample for one year after exposure, based on the sample before exposure, for the sheet installed at an antifouling inclination angle of 30 degrees
Was measured. A color reader CR-10 (measurement diameter: 8 mm) manufactured by Minolta Co., Ltd. was used for measuring the difference in lightness, and the measurement was performed on the day following the day when there was rainfall at the sampling time. Evaluation,
It carried out based on the following criteria. ◯: ΔL = −5 or more (little stain) Δ: ΔL = −10 or more and less than −5 (dirt) ×: ΔL = −10 or less (significantly stain) (2) Rain streak stain prevention vertical With respect to the sheet installed in the above, the state of occurrence of rain streak stains was visually observed and evaluated based on the following criteria. ◯: Almost no stain on the rain streak is observed. Δ: Light rain streaks are observed. X: Heavy rain stains are observed.

2. Weather resistance Using a Sunshine weather meter manufactured by Suga Test Instruments Co., Ltd. as a test sheet, a black panel temperature of 63 ° C. and a rainfall setting of 1
It was subjected to a weather resistance accelerated test under the condition of 8 minutes / 2 hours, and the appearance change of the antifouling layer was visually observed. The evaluation was performed based on the following criteria. ◯: No abnormality Δ: Slightly cracked in the antifouling layer ×: Significant crack or detachment in the antifouling layer

3. Heat loss measurement For the test sheet, the heat loss when hanging in a gear type air dryer at 100 ° C for 6 hours was calculated according to JIS-K6732-1981 by the following formula. The heating loss measurement was carried out on a sheet-shaped substrate on which an antifouling layer was not formed. The test piece used was cut out into a shape (No. 1 dumbbell) as described in JIS-K6732. The test pieces before and after the test were allowed to stand for 72 hours at room temperature in a desiccator using calcium chloride as a drying agent and dried, and then the mass was measured using a precision electronic balance manufactured by Ken Seiko Co., Ltd. EU-198A type. The calculated value is JI
Rounded to two decimal places by the method described in SZ-8401-1961.

[Equation 1]

[Synthesis of Polymer for Antifouling Resin Layer] Synthesis Example 1 (Synthesis of Antifouling Acrylic Resin 1) 50 parts by mass of N-methylol acrylamide, 50 parts by mass of 2-hydroxyethyl methacrylate, 4,4'-azobis- A solution of 10 parts by mass of 4-cyanovaleric acid, 3.4 parts by mass of 28% aqueous ammonia, and 200 parts by mass of water was added dropwise under nitrogen to 300 parts by mass of water at 95 ° C. in 5 hours, and further 4 hours. After continuing the reaction, 500 parts by mass of ethylene glycol monoethyl ether was added, and the reflux temperature was 1
Water was distilled off until the temperature reached 30 to 140 ° C. To this solution, 10.1 parts by mass of glycidyl methacrylate, 0.01 parts by mass of hydroquinone, and 0.05 parts by mass of N, N′-dimethyldodecylamine were added, and the reaction was carried out at 130 ° C. for 4 hours to obtain a vinyl group-terminated macromonomer of 2- An ethoxyethanol solution (nonvolatile content 25% by mass) was obtained. 120 parts by mass of a 25 mass% 2-ethoxyethanol solution of this macromonomer (30 parts by mass as macromonomer solid content), 50 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of methyl methacrylate, 40 parts by mass of toluene, ethylene glycol monomethyl. A solution of 20 parts by weight of ether and 0.3 parts by weight of azobisisobutyronitrile was added under nitrogen to 7
The polymerization reaction was carried out at 0 ° C. for 12 hours. The obtained composition was a uniform transparent liquid having a nonvolatile content of 41% by mass and an Mw of 110,000.

Synthesis Example 2 (Synthesis of Antifouling Acrylic Resin 2)
A solution comprising 30 parts by mass of N-methylolacrylamide, 70 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of 4,4′-azobis-4-cyanovaleric acid, 3.4 parts by mass of 28% ammonia water, and 200 parts by mass of water. Was added dropwise to 300 parts by mass of water at 95 ° C. under nitrogen for 5 hours, the reaction was continued for 4 hours, and then 500 parts by mass of ethylene glycol monoethyl ether was added.
Water was distilled off until the temperature reached 30 to 140 ° C. To this solution, 10.1 parts by mass of glycidyl methacrylate, 0.01 parts by mass of hydroquinone, and 0.05 parts by mass of N, N′-dimethyldodecylamine were added, and the reaction was carried out at 130 ° C. for 4 hours to obtain a vinyl group-terminated macromonomer of 2- An ethoxyethanol solution (nonvolatile content 25% by mass) was obtained. 120 parts by mass of a 25 mass% 2-ethoxyethanol solution of this macromonomer (30 parts by mass as macromonomer solid content), 50 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of methyl methacrylate, 40 parts by mass of toluene, ethylene glycol monomethyl. A solution of 20 parts by weight of ether and 0.3 parts by weight of azobisisobutyronitrile was added under nitrogen to 7
The polymerization reaction was carried out at 0 ° C. for 12 hours. The obtained composition was a uniform transparent liquid having a nonvolatile content of 41 mass% and an Mw of 100,000.

Synthesis Example 3 (Synthesis of Antifouling Acrylic Resin 3)
A solution consisting of 50 parts by mass of N-methylol acrylamide, 50 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of 4,4′-azobis-4-cyanovaleric acid, 3.4 parts by mass of 28% ammonia water, and 200 parts by mass of water. Was added dropwise to 300 parts by mass of water at 95 ° C. under nitrogen for 5 hours, the reaction was continued for 4 hours, then 500 parts by mass of ethylene glycol monoethyl ether was added, and the reflux temperature was 1%.
Water was distilled off until the temperature reached 30 to 140 ° C. To this solution, 10.1 parts by mass of glycidyl methacrylate, 0.01 parts by mass of hydroquinone, and 0.05 parts by mass of N, N′-dimethyldodecylamine were added, and the reaction was carried out at 130 ° C. for 4 hours to obtain a vinyl group-terminated macromonomer of 2- An ethoxyethanol solution (nonvolatile content 25% by mass) was obtained. 120 parts by mass of a 25 mass% 2-ethoxyethanol solution of this macromonomer (30 parts by mass as macromonomer solid content), 30 parts by mass of 2-hydroxyethyl methacrylate, 40 parts by mass of methyl methacrylate, 40 parts by mass of toluene, ethylene glycol monomethyl. A solution of 20 parts by weight of ether and 0.3 parts by weight of azobisisobutyronitrile was added under nitrogen to 7
The polymerization reaction was carried out at 0 ° C. for 12 hours. The obtained composition was a uniform transparent liquid having a nonvolatile content of 41 mass% and an Mw of 125,000.

Synthesis Example 4 50 parts by mass of N-methylolacrylamide, 50 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of 4,4'-azobis-4-cyanovaleric acid, 3.4 parts by mass of 28% ammonia water, and water. Under nitrogen, a solution consisting of 200 parts by mass was added dropwise to 300 parts by mass of water at 95 ° C. for 5 hours, and the reaction was continued for 4 hours. Then, 500 parts by mass of ethylene glycol monoethyl ether was added, and the reflux temperature was 1
Water was distilled off until the temperature reached 30 to 140 ° C. To this solution, 10.1 parts by mass of glycidyl methacrylate, 0.01 parts by mass of hydroquinone, and 0.05 parts by mass of N, N′-dimethyldodecylamine were added, and the reaction was carried out at 130 ° C. for 4 hours to obtain a vinyl group-terminated macromonomer of 2- An ethoxyethanol solution (nonvolatile content 25% by mass) was obtained. 120 parts by mass of a 25 mass% 2-ethoxyethanol solution of this macromonomer (30 parts by mass as macromonomer solid content), 70 parts by mass of methyl methacrylate, 40 parts by mass of toluene, 20 parts by mass of ethylene glycol monomethyl ether, azobisisobutyrate. A solution containing 0.3 part by mass of ronitrile was subjected to polymerization reaction at 70 ° C. for 12 hours under nitrogen. The obtained composition was a uniform transparent liquid having a nonvolatile content of 41 mass% and an Mw of 75,000.

Synthesis Example 5 70 parts by mass of 2-hydroxyethyl methacrylate, 30 parts by mass of 2-methoxyethyl methacrylate, 10 parts by mass of 4,4'-azobis-4-cyanovaleric acid, 80 parts by mass of methanol, and ethylene glycol monomethyl ether. Under nitrogen, a solution consisting of 120 parts by mass was added dropwise to 40 parts by mass of methanol at 80 ° C. and 260 parts by mass of 2-diethylene glycol over 5 hours, and the reaction was continued for 4 hours, and then the reflux temperature was 140 to 150 ° C. The solvent was distilled off until. To this solution, 10.1 parts by mass of glycidyl methacrylate, 0.015 parts by mass of hydroquinone, and 0.15 parts by mass of N, N′-dimethyldodecylamine were added, and the mixture was heated to 140 ° C.
The reaction was carried out for 4 hours to obtain an ethylene glycol monomethyl ether / diethylene glycol solution (nonvolatile content: 20% by mass) of a vinyl group-terminated macromonomer. 150 parts by weight of a 20% by weight ethylene glycol monomethyl ether / diethylene glycol solution of this macromonomer (30 parts as macromonomer solid content), 50 parts of 2-hydroxyethyl methacrylate, 20 parts of methyl methacrylate, 30 parts of toluene, azobisisobutyronitrile A solution of 0.3 parts was subjected to a polymerization reaction under nitrogen at 70 ° C. for 12 hours. The composition obtained was a uniform transparent liquid having a nonvolatile content of 41% and an Mw of 130,000.

Synthesis Example 6 50 parts by mass of N-methylol acrylamide and 50 parts by mass of hydroxyethyl methacrylate were mixed with 270 ion-exchanged water.
After dissolving in 0 parts by mass and removing the dissolved oxygen by nitrogen substitution, 0.2 g of water-soluble 2,2′-azobis (2-methylpropionamidine) dihydrochloride as an initiator was added, and the mixture was heated at 50 ° C. The reaction was carried out for 15 hours. The obtained composition was a uniform transparent liquid having a nonvolatile content of 4.0 mass% and an Mw of 135,000.

Example 1 As the base fabric, a non-coarse woven fabric made of polyester long fiber yarn having the following weave design was used. Both sides of this base cloth are coated with a polyurethane resin dispersion liquid for a waterproof resin layer of the following formulation 1 by a comma coater and dried at 120 ° C. for 5 minutes to give a waterproof resin layer having a total dry mass of 150 g / m ^2. Formed. <Formulation 1> 100 parts by mass of aqueous polyurethane resin (trademark: ADEKA BONTITER HUX-386, solid content concentration: 31% by mass, manufactured by Asahi Denka) 20 parts by mass of melamine isocyanurate (trademark: MC-640, average particle size: 1 ~ 5 μm, manufactured by Nissan Chemical Industries, Ltd.) Rutile type titanium oxide 5 parts by mass Calcium carbonate 10 parts by mass Thickener 0.5 parts by mass * All are shown in parts by mass in terms of solid content. Then, on one surface of the waterproof resin layer, the composition obtained in Synthesis Example 1 (antifouling acrylic resin 1) was coated by a gravure coater and dried at 130 ° C. for 2 minutes to give a dry mass of 4 g / m ^2. The antifouling resin layer was formed to obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 1.

Example 2 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, the composition of Synthesis Example 1 used for the antifouling resin layer was changed to the composition of Synthesis Example 2 (antifouling acrylic resin 2). The evaluation results of the obtained sheet are shown in Table 1.

Example 3 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, the composition of Synthesis Example 1 used for the antifouling resin layer was changed to the composition of Synthesis Example 3 (antifouling acrylic resin 3). The evaluation results of the obtained sheet are shown in Table 1.

Example 4 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, the composition of Synthesis Example 1 used for the antifouling resin layer was a commercially available antifouling acrylic resin (trademark: Chemitri L
H-448, main chain segment / side chain segment: 2-hydroxyethyl methacrylate, methyl methacrylate / N-methylol acrylamide, 2-hydroxyethyl methacrylate, solid content concentration: 25 mass%, manufactured by Soken Chemical Industry Co., Ltd.). The evaluation results of the obtained sheet are shown in Table 1.

Example 5 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, based on 100 parts by mass of the solid content of the antifouling acrylic resin 1 used for the antifouling resin layer, colloidal silica (trademark: Snowtex IPA-ST, solid content concentration: 3)
0 mass%, manufactured by Nissan Chemical Industries, Ltd.) was added in an amount of 100 mass parts in terms of solid content. The evaluation results of the obtained sheet are shown in Table 1.

Example 6 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, 30 parts by mass of silica (trademark: Aerosil 200, BET specific surface area: 200 g / m ² , manufactured by Nippon Aerosil) was added to 100 parts by mass of the solid content of the antifouling acrylic resin 1 used for the antifouling resin layer. did. The evaluation results of the obtained sheet are shown in Table 1.

Example 7 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, an acrylic copolymer (Trademark: P
UVA-30M, methyl methacrylate copolymerization rate: 70
Mass%, manufactured by Otsuka Chemical Co., Ltd.) was added. The evaluation results of the obtained sheet are shown in Table 1.

Example 8 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 1. However, with respect to 100 parts by mass of the solid content of the antifouling acrylic resin 1 used for the antifouling resin layer, zinc oxide ultrafine particles (trademark: ZnO-100, average particle diameter: 0.015 μm)
m, manufactured by Sumitomo Osaka Cement). The evaluation results of the obtained sheet are shown in Table 1.

Example 9 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 1. However, an acrylic copolymer (trademark: Chemitry LF) in which a fluorine-based compound is copolymerized with 100 parts by mass of the solid content of the antifouling acrylic resin 1 used for the antifouling resin layer
-700, main chain segment / side chain segment: methyl methacrylate, perfluoroalkyl methacrylate /
Methyl methacrylate, solid content concentration: 7.5% by mass, manufactured by Soken Chemical Co., Ltd.) was added in an amount of 10 parts by mass in terms of solid content. The evaluation results of the obtained sheet are shown in Table 1.

Comparative Example 1 A comparative sheet was prepared in the same manner as in Example 1. However, the composition of Synthesis Example 1 used for the antifouling resin layer was changed to the composition of Synthesis Example 4. The evaluation results of the obtained sheet are shown in Table 1.

Comparative Example 2 A comparative sheet was prepared in the same manner as in Example 1. However, the composition of Synthesis Example 1 used for the antifouling resin layer was changed to the composition of Synthesis Example 5. The evaluation results of the obtained sheet are shown in Table 1.

Comparative Example 3 A comparative sheet was prepared in the same manner as in Example 1. However, the composition of Synthesis Example 1 used for the antifouling resin layer was changed to the composition of Synthesis Example 6 (a stock solution having a solid content concentration of 4% by mass was used after being concentrated to a solid content concentration of 10% by mass). did. The evaluation results of the obtained sheet are shown in Table 1.

[0070]

[Table 1]

As is clear from Table 1, the sheets of Examples 1 to 9 had good antifouling properties. Examples 5 and 6
Since the sheets of No. 1 and No. 3 were added with colloidal silica and silica, respectively, they exhibited excellent antifouling properties. Further, the sheets of Examples 7 and 8 were excellent in weather resistance because the acrylic copolymer and the ultrafine zinc oxide particles each having an ultraviolet absorbing property were added thereto. On the other hand, in the sheet of Comparative Example 1, the main chain segment was not copolymerized with the hydroxyalkyl (meth) acrylate-based compound portion, and thus the antifouling property was not sufficient. In the sheet of Comparative Example 2, the N-methylol (meth) acrylamide compound was not copolymerized in the branch chain segment, so the weather resistance was not sufficient. The sheet of Comparative Example 3 was not a comb-type copolymer, and thus did not have sufficient antifouling property.

Example 10 As a base fabric, a non-coarse woven fabric made of propylene short fiber base fabric yarn having the following weave design was used. <Polypropylene non-coarse woven fabric> 492 dtex × 492 dtex (24 ^s / 2 × 24 ^s / 2) ────────────────────────── 35 × 36 (Book / 25.4 mm) Waterproof resin by laminating ethylene-vinyl acetate copolymer resin film (thickness 0.15 mm) for waterproof resin layer of the following formulation 2 formed by calendering on both sides of this base cloth Layer (1) was formed. <Formulation 2> Ethylene-vinyl acetate copolymer resin 100 parts by mass (vinyl acetate copolymerization rate: 19% by mass) Red phosphorus 20 parts by mass Aluminum hydroxide 10 parts by mass Rutile titanium oxide 5 parts by mass Hindered phenolic antioxidant Agent 0.2 parts by mass Phosphate ester-based lubricant 0.5 parts by mass Next, for one of the waterproof resin layers (1), a waterproof resin layer of the following formulation 3 is formed by calendering to a thickness of 0.5 mm. Heat-laminating film to form waterproof resin layer (2)
Was formed to produce a sheet-shaped base material. <Formulation 3> Ethylene-vinyl acetate copolymer resin 80 parts by mass (vinyl acetate copolymerization rate: 19% by mass) Maleic anhydride-modified polyethylene resin 20 parts by mass Magnesium hydroxide 50 parts by mass Rutile titanium oxide 5 parts by mass Hindered amine system Light stabilizer 0.5 parts by mass Hindered phenolic antioxidant 0.2 parts by mass Phosphate ester lubricant 0.5 parts by mass Corona discharge on the surface of the waterproof resin layer (2) of this sheet-shaped substrate in air After the treatment, the composition (antifouling acrylic resin 1) obtained in Synthesis Example 1 was coated with a gravure coater and dried at 130 ° C. for 2 minutes to give an antifouling resin layer having a dry mass of 4 g / m ^2. To obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 2.

Example 11 The polypropylene non-coarse woven fabric used in Example 10 was used as a base fabric, and both sides of the woven fabric of the base fabric were molded by calendering, and chlorinated polyethylene for a waterproof resin layer of the following formulation 4 was used. A resin film (thickness: 0.20 mm) was laminated to form a waterproof resin layer, and a sheet-shaped substrate was produced. <Formulation 4> 100 parts by mass of chlorinated polyethylene resin (Trademark: ALCRYN 2080 NC, manufactured by DuPont Mitsui Polychemicals) Rutile titanium oxide 5 parts by mass Organotin stabilizer 2 parts by mass Hindered phenolic antioxidant 0.2 Parts by mass Phosphate ester lubricant 0.2 parts by mass On one surface of the waterproof resin layer of this sheet-shaped substrate, the composition (antifouling acrylic resin 1) obtained in Synthesis Example 1 is coated by a gravure coater, By drying at 0 ° C. for 2 minutes, an antifouling resin layer having a dry mass of 4 g / m ² was formed to obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 2.

Example 12 The polyester non-coarse woven fabric used in Example 1 was used as a base cloth, and both surfaces of the base cloth were dip-processed with a fluorine-containing resin dispersion for an adhesive layer having the following composition 5 at 120 ° C. 5
20 g / m ^{2 in} total dry mass by drying for 1 minute
The adhesive layer of was formed. <Formulation 5> Tetrafluoroethylene-6-fluoropropylene-fluoride 100 parts by mass Vinylidene copolymer resin (trademark: THV-350C, solid content concentration: 5% by mass, manufactured by Sumitomo 3M) Silane coupling agent 5 parts by mass * All are shown in parts by weight calculated as solid content. Next, a waterproof resin layer was formed by thermally laminating a film for a waterproof resin layer having the following Formulation 6 formed by calendering to a thickness of 0.2 mm on both surfaces of this adhesive layer to form a sheet-like base material. <Formulation 6> Tetrafluoroethylene-6-fluoropropylene-fluoride 100 parts by mass Vinylidene copolymer resin (trademark: THV-400G, manufactured by Sumitomo 3M) Phosphate ester-based lubricant 0.5 parts by mass Hindered phenol-based oxidation Inhibitor 0.2 parts by mass The composition obtained in Synthesis Example 3 (antifouling acrylic resin 3) is coated on one side of the sheet-shaped substrate with a gravure coater and dried by drying at 130 ° C. for 2 minutes. An antifouling resin layer having a mass of 4 g / m ² was formed to obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 2.

Example 13 The non-coarse polyester woven fabric used in Example 1 was used as a base fabric, and both sides of this adhesive layer were molded by an extrusion molding machine (T die) to a thickness of 0.2 mm. The waterproof resin layer was formed by laminating the polyester film for a waterproof resin layer of 1 above to prepare a sheet-shaped substrate. <Compound 7> Polyester resin 100 parts by mass (Trademark: Perprene P-40B, manufactured by Toyobo) Resorcinol bisdiphenyl phosphate condensate 15 parts by mass (Trademark: Philolflex RDP, manufactured by Akzo Kashima) Rutile type titanium oxide 5 parts by mass Hinder Dephenol-based antioxidant 0.2 parts by mass Carbodiimide (hydrolysis inhibitor) 0.5 parts by mass (Trademark: Stavaxol P-100, Sumitomo Bayer Urethane) Polyolefin-based lubricant 0.2 parts by mass The composition obtained in Synthesis Example 1 (antifouling acrylic resin 1) was coated on one surface with a gravure coater and dried at 130 ° C. for 2 minutes to form an antifouling resin layer having a dry mass of 4 g / m ^2. Then, an antifouling waterproof sheet of the present invention was obtained. The evaluation results of the obtained sheet are shown in Table 2.

Example 14 A non-coarse woven fabric made of an aliphatic polyester (polylactic acid type) fiber yarn having the following woven structure was used as the base fabric. <Aliphatic polyester non-coarse woven fabric> 246 dtex / 2 × 246 dtex / 2 (24 ^s / 2 × 24 ^s / 2) ──────────────────────── ─────── 40 × 40 (pieces / 25.4mm) Both sides of this base cloth are coated with the aliphatic polyester resin dispersion liquid for waterproof resin layer of the following formulation 8 by a comma coater, and at 5 ° C at 120 ° C. By drying for a minute, a waterproof resin layer having a total dry mass of 150 g / m ² was formed to prepare a sheet-shaped substrate. <Formulation 8> 70 parts by mass of aqueous aliphatic polyester resin (trademark: Randy CP-05A, solid content concentration: 40% by mass, manufactured by Miyoshi Yushi Co., Ltd.) 30 parts by mass of aqueous vinyl acetate-ethylene copolymer resin (trademark: Sumikaflex 752 , Solid content concentration: 50% by mass, manufactured by Sumitomo Chemical Co., Ltd. Melamine-coated ammonium polyphosphate 10 parts by mass (trademark: TERAGE C-60, average particle diameter: 7.5 μm, manufactured by Chisso) benzoguanamine 10 parts by mass (trademark: Eposter GP- 50, average particle diameter: 5 μm, manufactured by Nippon Shokubai Co., Ltd.) Oxazoline-based curing agent 2 parts by mass Rutile titanium oxide 5 parts by mass Hindered phenol-based antioxidant 0.2 parts by mass Thickener 1 part by mass * All in terms of solid content Displayed in parts by mass. The composition obtained in Synthesis Example 1 (antifouling acrylic resin 1) was coated on one side of this sheet-shaped substrate with a gravure coater and dried at 130 ° C. for 2 minutes to give a dry mass of 4 g / m ² . An antifouling resin layer was formed to obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 2.

Example 15 For the waterproof resin layer of the following formulation 9, the polyester non-coarse woven fabric used in Example 1 was used as the base fabric, and both sides of this base fabric were molded by calendering to a thickness of 0.2 mm. A vinyl chloride-vinyl acetate copolymer resin film was laminated to form a waterproof resin layer, and a sheet-shaped substrate was produced. <Formulation 9> Vinyl chloride-vinyl acetate copolymer resin 100 parts by mass Antimony trioxide 10 parts by mass Rutile type titanium oxide 5 parts by mass Ba-Zn-based stabilizer 2 parts by mass Hindered phenol-based antioxidant 0.2 parts by mass The composition obtained in Synthesis Example 1 (antifouling acrylic resin 1) was coated on one side of this sheet-shaped substrate with a gravure coater and dried at 130 ° C. for 2 minutes to give a dry mass of 4 g / m ² . An antifouling resin layer was formed to obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 2.

[0078]

[Table 2]

As is clear from Table 2, Examples 10 to 1
The sheet of No. 5 showed good antifouling property regardless of the type of the waterproof resin layer.

Example 16 The polyester non-coarse woven fabric used in Example 1 was used as a base cloth, and both surfaces of the base cloth were coated with a polyvinyl chloride resin dispersion for adhesive layers having the following composition 10 to coat 180
The total dry mass is 80 by heat treatment at ℃ for 2 minutes.
An adhesive layer of g / m ² was formed. <Formulation 10> Polyvinyl chloride resin for paste processing 100 parts by mass Tris-2-ethylhexyl trimellitate 80 parts by mass (molecular weight: 547) Epoxidized soybean oil 3 parts by mass Organotin stabilizer 2 parts by mass Hindered phenolic oxidation Inhibitor 0.2 parts by mass Antimony trioxide 10 parts by mass Then, a polyvinyl chloride resin film for waterproof resin layer having the following composition 11 formed by calendering to a thickness of 0.2 mm is laminated on both surfaces of the adhesive layer. To form a waterproof resin layer to produce a sheet-shaped substrate. <Compound 11> Polyvinyl chloride resin for calendering 100 parts by mass Diisodecyl phthalate (DIDP) 60 parts by mass (molecular weight: 446) Ba-Zn stabilizer 2 parts by mass Phosphite stabilizer 1 part by mass Hindered phenolic oxidation Inhibitor 0.2 parts by weight Antimony trioxide 10 parts by weight Rutile type titanium oxide 5 parts by weight On one side of this sheet-shaped substrate, based on 100 parts by weight of the solid content of the antifouling acrylic resin 1 used in Example 1. , Colloidal silica (trademark: Snowtex IPA-ST, solid content concentration: 30 mass%, manufactured by Nissan Chemical Industries, Ltd.) was added to 100 parts by mass in terms of solid content, and the coating solution was coated with a gravure coater at 130 ° C. By forming the antifouling resin layer having a dry mass of 4 g / m ² by drying for 2 minutes,
The antifouling waterproof sheet of the present invention was obtained. The evaluation results of the obtained sheet are shown in Table 2.

Example 17 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 16. However, the diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was replaced with diisodecyl adipate (D).
IDA, molecular weight: 427) Changed to 60 parts by mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 18 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 16. However, the diisodecyl phthalate (60 parts by mass) used as the plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of Formulation 10 was changed to epoxidized soybean oil (70 parts by mass). The evaluation results of the obtained sheet are shown in Table 3.

Example 19 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 16. However, the diisodecyl phthalate (60 parts by mass) used as the plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was changed to tris-2-ethylhexyl trimellitate (70 parts by mass). The evaluation results of the obtained sheet are shown in Table 3.

Example 20 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 16. However, the diisodecyl phthalate (60 parts by mass) used as the plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was changed to tetra-2-ethylhexyl pyromellitic acid (70 parts by mass). The evaluation results of the obtained sheet are shown in Table 3.

Example 21 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 16. However, diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was mixed with pentaerythritol ester plasticizer (trademark: UL-6, manufactured by Asahi Denka) 70 parts by mass I changed to the department. The evaluation results of the obtained sheet are shown in Table 3.

Example 22 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 16. However, diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for a waterproof resin layer of the above-mentioned formulation 10 was used as an adipic acid polyester plasticizer (trademark: PN-400, molecular weight: 2000, Asahi Denka Co., Ltd.). Manufactured) to 70 parts by mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 23 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 16. However, a urethane polymer (trademark: Pandex T-5275N, manufactured by Dainippon Ink and Chemicals, Inc.) )
Changed to 70 parts by mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 24 The antifouling waterproof sheet of the present invention was produced in the same manner as in Example 16. However, diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for waterproof resin layer of the above-mentioned formulation 10 was mixed with ethylene-vinyl acetate-carbon monoxide terpolymer (trademark: Elvalloy 742, Mitsui DuPont Polychemical) changed to 100 parts by mass.
The evaluation results of the obtained sheet are shown in Table 3.

Example 25 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 16. However, diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was mixed with ethylene-acrylic acid ester-carbon monoxide terpolymer (trademark: Elvalloy HP5).
53, manufactured by DuPont Mitsui Polychemical) 100 mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 26 An antifouling waterproof sheet of the present invention was produced in the same manner as in Example 16. However, the diisodecyl phthalate (60 parts by mass) used as the plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was mixed with diisononyl phthalate (DI
NP, molecular weight: 418) changed to 60 mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 27 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 16. However, the diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for the waterproof resin layer of the above-mentioned formulation 10 was mixed with dioctyl phthalate (DO).
P, molecular weight: 390) 60 parts by mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 28 An antifouling waterproof sheet of the present invention was prepared in the same manner as in Example 16. However, diisodecyl phthalate (60 parts by mass) used as a plasticizer in the polyvinyl chloride resin film for a waterproof resin layer of the above-mentioned formulation 10 was replaced with diheptyl phthalate (DH).
P, molecular weight: 362) changed to 60 parts by mass. The evaluation results of the obtained sheet are shown in Table 3.

Example 29 In the same manner as in Example 16, an antifouling waterproof sheet of the present invention was obtained. However, an additive migration prevention layer having a dry mass of 4 g / m ² was obtained by coating an additive migration prevention layer coating solution having the following composition 11 on a waterproof resin layer with a gravure coater and drying at 120 ° C. for 2 minutes. Then, the antifouling resin layer was formed. The evaluation results of the obtained sheet are shown in Table 3. <Formulation 11> 100 parts by mass of primary amino group-containing acrylic resin (trademark: Polyment NK-380, solid content concentration: 30% by mass, manufactured by Nippon Shokubai Co., Ltd.) 10 parts by mass of bisphenol A type epoxy resin (trademark: Epicoat 828, oil conversion Made of shell) * All are shown in parts by mass in terms of solid content.

Example 30 The polyester non-coarse woven fabric used in Example 1 was used as a base fabric, and both surfaces of the base fabric were coated with an acrylic resin dispersion liquid for a waterproof resin layer having the following composition 12 to prepare 180
The total dry mass is 20 by heat treatment at ℃ for 5 minutes.
A waterproof resin layer of 0 g / m ² was formed to prepare a sheet-shaped base material. <Composition 12> Acrylic resin for paste processing 100 parts by mass (trademark: Zeon acrylic resin F320, manufactured by Nippon Zeon) 60 parts by mass tricresyl phosphate (TCP) 20 parts by mass tributyl acetylcitrate (ATBC) 5 parts by mass rutile titanium oxide Parts hindered phenolic antioxidant 0.2 parts by weight cyanoacrylate ultraviolet absorber 0.2 parts by weight An additive migration prevention layer of the above composition 11 is coated on the waterproof resin layer by a gravure coater, and 120
Dry mass is 4g / m ² by drying at ℃ for 2 minutes
The additive migration prevention layer of 1 was formed. Then, on the additive migration preventing layer, 100 parts by mass of the solid content of the antifouling acrylic resin 1 used in Example 1 was used, and colloidal silica (trademark:
Snowtex IPA-ST, solid content concentration: 30 mass%, manufactured by Nissan Chemical Industries, Ltd.) is added to 100 parts by mass in terms of solid content, and the coating solution is coated with a gravure coater and dried at 130 ° C. for 2 minutes. An antifouling resin layer having a dry mass of 4 g / m ² was formed to obtain an antifouling waterproof sheet of the present invention. The evaluation results of the obtained sheet are shown in Table 3.

Comparative Example 4 A comparative sheet was prepared in the same manner as in Example 16. However,
For the antifouling resin layer, a 6: 4 mixture of vinylidene fluoride polymer and methyl methacrylate polymer (trademark: Hycorp AF-
471, solid content concentration: 10% by mass, manufactured by Special Colorants Industry) was used. The evaluation results of the obtained sheet are shown in Table 3.

[0096]

[Table 3]

As is clear from Table 3, Examples 16-2
The sheet of No. 9 used the antifouling acrylic resin for the antifouling resin layer, and therefore had excellent antifouling property despite using the soft polyvinyl chloride resin for the waterproof resin layer. In particular, the sheets of Examples 23 to 25 were excellent in antifouling property because the polymer plasticizer was used. Further, since the additive migration prevention layer was formed on the sheet of Example 29, Example 16 in which the additive migration prevention layer was not formed was used.
The sheet showed even better antifouling properties than the above sheet. Example 3
In the sheet No. 0, an acrylic resin containing a plasticizer was used for the waterproof resin layer, but since the additive migration prevention layer was formed, the antifouling property was good. On the other hand, in the sheet of Comparative Example 4, a fluorine-containing resin having an excellent plasticizer migration-preventing property was used in the antifouling resin layer, but the antifouling property was poor.

Example 31 The antifouling waterproof sheet of Example 1 was wound around a paper tube having a diameter of 5.08 cm with the antifouling resin layer inside (sheet length: 40 cm), and the antifouling property of the present invention was obtained. A roll-shaped roll of a waterproof sheet was obtained. This roll-shaped roll was left in an oven set to 50 ° C.-90% relative humidity for 2 weeks,
An accelerated test was conducted. Table 4 shows the antifouling property evaluation results of the sheets after the acceleration test.

Example 32 The antifouling waterproof sheet of Example 16 was used as a roll-up roll in the same manner as in Example 31. The evaluation results are shown in Table 4.

Example 33 The antifouling waterproof sheet of Example 25 was used in the same manner as in Example 31 to prepare a rolled-up body. The evaluation results are shown in Table 4.

Example 34 In the same manner as in Example 29, an antifouling waterproof sheet of the present invention was obtained. However, the additive migration prevention layer of Formulation 11 was formed on both surfaces of the waterproof resin layer (the antifouling resin layer was on only one surface). The obtained sheet was made into a rolled-up body in the same manner as in Example 31. The evaluation results are shown in Table 4.

[0102]

[Table 4]

The rolled-up body of Example 31 contained no plasticizer and no softening agent in the waterproof resin layer, and therefore had good antifouling property after acceleration. The roll-shaped roll of Example 32 contained a plasticizer in the waterproof resin layer, and therefore exhibited good antifouling properties when the acceleration time was short, but exhibited antifouling properties when the acceleration time was long, A decrease in the rain line stain prevention property was observed. In the roll-shaped roll of Example 33, the polymer plasticizer was used in the waterproof resin layer, and therefore the stain resistance was slightly reduced. In the roll-shaped roll of Example 34, since the additive migration preventing layer was formed also on the back surface of the sheet, the deterioration of the antifouling property due to the acceleration was suppressed.

[0104]

The antifouling waterproof sheet of the present invention has excellent antifouling property due to the formation of the antifouling resin layer containing the antifouling acrylic resin, and in particular, the rain line antifouling property is excellent. Is. INDUSTRIAL APPLICABILITY The antifouling tarpaulin of the present invention can be used for industrial materials such as medium / large tents, tent warehouses, eaves tents, truck hoods, backlits for signs, etc. even when used for long periods of time to prevent rain line stains. Because it can maintain a beautiful appearance that is not
It is extremely useful in practice.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 55/00 C08L 55/00 D06M 15/29 D06M 15/29 15/564 15/564 // (C08L 55 / 00 C08L 33:04 33:04) F-term (reference) 4F100 AA08 AA20C AA20E AA21 AH02B AH02D AH07C AH07E AK01B AK01D AK03B AK03D AK10B AK10D AK15B AK15D AK17B AK17D AK25B AK25C AK25D AK25E AK26C AK26E AK41 AK41B AK41D AK51B AK51D AK53B AK53D AK62B AK62D AK66B AK66D AK68B AK68D AK71B AK71D AK80B AK80D AL01C AL01E BA03 BA05 BA06 BA07 BA10A BA10C BA10E BA13 CA04B CA04D CA07C CA07E CA25B CA25D DE01C DE01E DG01A DG04 DG11A DG12 EH46 GB90 JA07B JA07D JD05 JD05B JD05D JD09C JD09E JD14C JD14E JL06 JL06C JL06E JL09 YY00B YY00C YY00D YY00E 4J002 BB062 BB072 BD031 BG072 BN111 BQ001 CD002 CF002 CK022 DE107 DJ016 EH046 EH096 EH146 FD016 FD 022 FD026 FD207 GF00 4J027 AA02 BA02 BA07 BA08 CB09 CC02 CD08 4L033 AA07 AA08 AB05 AB06 AC03 AC04 AC15 CA12 CA15 CA18 CA24 CA29 CA45 CA50 DA06

Claims (10)

[Claims] 1. A sheet-like base material comprising a base cloth containing a fiber cloth, and a waterproof resin layer formed on at least one surface of the base cloth and containing a waterproof resin, and the sheet-like base material. And an antifouling resin layer formed on the waterproof resin layer and containing an antifouling acrylic resin, wherein the antifouling acrylic resin of the antifouling resin layer is one polymer main chain per molecule. A segment, comprising a comb-type copolymer composed of a plurality of polymer branch chain segments branch-bonded to the polymer main chain segment, the polymer main chain segment as the main component , A hydroxyalkyl (meth) acrylate and a (meth) acrylic acid ester copolymer residue, wherein the polymer branched chain segment is N-
An antifouling waterproof sheet comprising a copolymer residue of methylol (meth) acrylamide and hydroxyalkyl (meth) acrylate. 2. The antifouling waterproof sheet according to claim 1, wherein the antifouling resin layer further contains 10 to 200 parts by mass of colloidal silica with respect to 100 parts by mass of the antifouling acrylic resin. 3. The antifouling resin layer comprises (1) zinc oxide ultrafine particles having an average particle size of 0.1 μm or less, and (2) at least one kind selected from benzotriazole compounds and benzophenone compounds. The antifouling waterproof sheet according to claim 1 or 2, further comprising at least one selected from a copolymer containing a copolymerized unit formed from an ultraviolet absorbing monomer. 4. The waterproof resin layer comprises polyvinyl chloride resin, polyolefin resin, chlorinated polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene-
A (meth) acrylic acid ester-based copolymer resin, a polyurethane-based resin, a polyester-based resin, an acrylic-based resin, and one or more selected from a fluorine-containing resin.
The antifouling waterproof sheet material according to any one of 3 above. 5. The waterproof resin layer further contains an additive, and an additive migration preventing layer is formed between the additive-containing waterproof resin layer and the antifouling resin layer. Four
The antifouling waterproof sheet according to any one of 1. 6. The back surface waterproof resin layer formed on the back surface of the base fabric further contains an additive, and the additive migration prevention layer is formed on the additive-containing back surface waterproof resin layer. The antifouling waterproof sheet according to any one of items 1 to 5. 7. The additive migration prevention layer comprises a polyolefin resin, an ethylene-vinyl acetate copolymer resin, an ethylene- (meth) acrylic acid ester copolymer resin, a fluorine-containing resin, an acrylic resin, urethane. The antifouling waterproof sheet according to claim 5 or 6, which comprises one or more kinds of synthetic resins selected from resin series and polyester series resins. 8. The waterproof resin layer comprises: (1) a polyvinyl chloride resin; (2) a phthalate ester plasticizer having a molecular weight of 400 or more; an aliphatic dibasic acid ester plasticizer having a molecular weight of 420 or more; Meritic acid ester-based plasticizer, pyromellitic acid ester-based plasticizer, dipentaerythritol ester-based plasticizer, epoxy-based plasticizer, polyester plasticizer having a molecular weight of 600 or more, ester-based urethane polymer,
An ethylene-vinyl acetate-carbon monoxide terpolymer, and a plasticizer containing one or more selected from an ethylene- (meth) acrylic acid ester-carbon monoxide terpolymer. The antifouling waterproof sheet according to any one of items 1 to 7. 9. The JIS K-67 of the sheet-shaped base material.
The antifouling waterproof sheet according to any one of claims 1 to 8, wherein the weight loss on heating for 6 hours at 100 ° C ± 2 ° C according to 32-1981 is 1.0% or less. 10. The antifouling waterproof sheet according to any one of claims 1 to 9, which is wound up in a roll shape.