JP2005219267A - Anti-staining film material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-staining film material excellent in anti-staining properties, light transmissivity, flexibility and abrasion resistance by coating a fiber base material with a thermoplastic resin such as a fluoroplastic resin, an acrylic resin or the like. <P>SOLUTION: The anti-staining film material is constituted by combounding the fiber base material and a silane type coating agent and cured/solidfied by the catalytic action of the silane type coating agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a long-term antifouling property and abrasion resistance, and good light transmission, water repellency, flexibility, and abrasion resistance, in which a resin and a silane coating agent are fixed to a fiber base material. Anti-fouling film material, medium and large tent sheet, eaves tent sheet, decorative tent sheet, building tent sheet, building work sheet, tent warehouse sheet, automobile hood sheet, The present invention relates to an antifouling film material useful as a flexible container sheet, a signboard backlit sheet, and a tarpaulin sheet.

Conventionally, a film material in which a soft vinyl chloride resin having various advantages such as low cost, easy handling such as workability, and easy high-frequency welder welding is applied to a fiber base has been proposed. Various plasticizers blended to improve the flexibility of the vinyl-based resin migrate to the surface of the film material, and there is a problem that dirt tends to adhere to increase adhesion, making it difficult to remove.
In order to remedy such drawbacks, as described in JP-A-11-291415 (Patent Document 1), a soft vinyl chloride resin is applied to a fiber base material and further coated with vinylidene fluoride resin via an adhesive. However, film materials with improved adhesion and antifouling properties have been proposed, but the flexibility and light transmission of the film material due to the lamination of the resin is insufficient, and the cost increases. was there.
In JP-A-10-202800 (Patent Document 2), an acrylic resin and a urethane resin are applied to a fiber base material to improve water resistance. There was a problem that the adhesion of dirt was concerned and sufficient antifouling property could not be obtained. Moreover, in order to impart flame retardancy, a flame retardant is mixed in the urethane resin, but there is a problem that the environmental load is high.

  Membrane materials represented by tents, etc. need to be antifouling because they lose their aesthetics due to the attachment of dirt such as smoke and dust in the atmosphere due to long-term outdoor use, and they are used in various places in various forms. Flexibility is also required to Recently, it has been required to improve daylighting in outdoor sports facilities, etc., to implement various sports in a bright atmosphere, reduce temperature control costs, grow natural turf, etc., and have sufficient light transmittance. . In addition, there is an urgent need to improve the wear resistance of the film material surface in order to solve the problem of shortening the life of the film material surface, which is a concern when cleaning tents and the like.

JP 11-291415 A JP-A-10-202800

  In view of the background of such prior art, the present invention has a problem of deterioration of antifouling property caused by applying a thermoplastic resin such as a fluorine-based resin or an acrylic resin to a fiber base material, and the conventional flexibility of the fiber base material. The film | membrane material which improved the fall of property and the fall of the light transmittance is provided.

The present invention is a composite of a fiber base material, a resin, and a silane-based coating agent composed mainly of a compound represented by the following formula 1 (hereinafter also referred to as “compound 1”), and the silane-based coating agent is a catalyst. It is related with the antifouling film | membrane material characterized by being hardened and solidified by the effect | action of.

(In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a number of 2 to 10)

  Since the antifouling film material using the coating agent of the present invention is water-repellent, it keeps the antifouling effect for a long period of time, especially when used outdoors, because it does not leave scale deposits or rain streaks due to rainwater. can do. Further, in addition to the antifouling property, it is possible to impart light transmittance, flexibility and wear resistance at the same time, thereby enabling the multifunctional film material.

In the present invention, as shown in the above formula 1, the fiber substrate is coated with a compound containing as a repeating unit one of the four substituents of the silicon atom that is substituted with a non-hydrolyzable substituent. By doing so, the problems found in the prior art are solved. The compound of the formula 1 has less than one strong siloxane bond with the adjacent silicon atom as compared with the conventionally used tetraalkoxysilane, but there is an unreacted bond correspondingly. In other words, since it remains in the form of “dangling”, the flexibility of the coating film can be maintained, and as a result, the flexibility of the film material can be maintained.
Further, R ₄ in Formula 1 does not hydrolyze even if the compound of Formula 1 undergoes the subsequent hydrolysis / polycondensation reaction, so that organicity is imparted to the manufactured coating film, and as a result, the film The material is organic, that is, water-repellent.

  As described above, the raw material (monomer) for obtaining the compound of Formula 1 can be purchased at a similar level compared with tetraalkoxysilane which is inexpensive but has strong inorganic properties. Therefore, by using the compound of Formula 1, it is possible to produce a film material having a film having sufficient organicity and sufficient strength without using an expensive so-called silane coupling agent. . As described above, the present invention is characterized by using the compound represented by the formula 1 in order to achieve the above object.

In the present invention, a fiber base material and a resin layer typified by a cloth material such as a nonwoven fabric or a woven fabric, and a coating agent mainly composed of a compound represented by Formula 1 are applied, and this is cured and solidified by the action of a catalyst. The fiber base material, the resin layer, and the coating agent are integrally combined.
R ₁ , R ₂ , R ₃ and R ₄ in Formula 1 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a number from 2 to 10.
Such a compound 1 can be obtained by condensing a monomer (alkyltrialkoxysilane, for example, methyltrimethoxysilane). The main chain repeats are n = 2 to 10. When n = 1, that is, when a monomer is used, it takes a long time to polymerize, and a coat film having sufficient strength can be produced in a short time. This is because there are difficult aspects. However, when n is 11 or more, the number of alkoxy groups for polymerization on the fiber substrate is insufficient when applied to the fiber substrate, and a coated film having sufficient strength is produced. It becomes difficult. Therefore, in the present invention, the compound of formula 1 is a condensate of n = 2 to 10, especially n = 2 to 8.

  In general, when synthesizing a condensate of formula 1 and n of 2 or more from a monomer, it is technically impossible to accurately control the degree of polymerization. Therefore, in the present invention, the meaning of using n = 2 to 10, more preferably n = 2 to 8, means that n is mainly 2 to 10, preferably mainly 2 to 8 in view of the degree of polymerization distribution. For example, it is possible to use a coating agent in which a compound is contained. For example, a compound having n of 11 or more may be contained.

  Specific examples of the compound represented by Formula 1 include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane. Examples include condensates of monomers such as ethoxysilane, methyltripropoxysilane, and ethyltripropoxysilane. In addition, the compound of Formula 1 may be a product obtained by condensing only one kind of such a monomer, or may be a product obtained by condensing two or more kinds of the above exemplified monomers.

The primary role of the non-hydrolyzable substituent (R ₄ ) in the compound of formula 1 is to impart flexibility to the coating film, but at the same time, to impart water repellency to the coating film. For example, R ₄ is preferably an alkyl group. In general, as the number of carbon atoms increases, the organic substituent increases in organic properties, that is, water repellency. However, if the carbon number is too large, distortion occurs in the coating film due to steric hindrance, which causes a decrease in film strength. . Therefore, the number of carbon atoms in the alkyl group and the type and amount of each monomer constituting the compound of formula 1 (condensate) are determined by conducting preliminary production tests while referring to the examples of this specification. Is preferably determined. The carbon number of the alkyl group of R ₄ is usually 1-4. However, imparting water repellency to the coating film can also be achieved by adding a compound represented by formula 2 (trialkoxysilanes) and / or a compound represented by formula 3 (dialkoxysilanes) described later. In this case, it is not essential that R ₄ in the compound of Formula 1 is an alkyl group, and it may be a hydrogen atom.

  In the present invention, in addition to the compound of the formula 1, a coating agent containing a compound of the following formula 2 (hereinafter also referred to as “compound 2”) and / or a compound of the following formula 3 (hereinafter also referred to as “compound 3”) is used. it can.

(In Formula 2, R ₅ , R ₆ and R ₇ are the same or different and each represents a hydrogen atom, an alkyl group or an alkenyl group, and R ₈ is an alkyl which may contain an epoxy group or a glycidyl group in the molecule. Group, alkenyl group or phenyl group.)

(In Formula 3, R ₉ and R ₁₁ are the same or different and each represents a hydrogen atom, an alkyl group or an alkenyl group, and R ₁₀ and R ₁₂ may contain an epoxy group or a glycidyl group in the molecule. An alkyl group, an alkenyl group or a phenyl group.)

Here, the compound of Formula 2 may be two or more of such monomers. Moreover, the compound of Formula 2 may be a condensate of two or more molecules obtained by condensing one or more of such monomers. However, the compound shown in Formula 1 is excluded.
In the present invention, by using a coating agent containing the compound of the above formula 2 in addition to the compound of the formula 1, the organic compound etc. possessed by the compound of the formula 2 can be compared with the film material produced without using it. It is possible to newly impart properties or increase properties such as organic properties. The compound of the formula 2 added for this purpose is a compound consisting of 4 substituents, in which 3 are hydrolyzable substituents and the remaining 1 is non-hydrolyzable substituents.
In Formula 2, R ₅ , R ₆ and R ₇ may be the same or different and each is a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms, and R ₈ is an epoxy group in the molecule. Or it is a C1-C10 alkyl group, alkenyl group, or phenyl group which may contain the glycidyl group.

  Specific examples of the compound represented by Formula 2 include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, vinyltriethoxysilane, phenyl Single quantities of triethoxysilane, γ- (methacryloxypropyl) triethoxysilane, γ-glycidoxypropyltriethoxysilane, aminopropyltriethoxysilane, vinyltris (βmethoxyethoxy) silane Body, vinyltrimethoxysilane, phenyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, β- (3,4 epoxy cyclohexyl) ethyl Trimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, γ- (methacryloxypropyl) triethoxysilane, γ-glycidoxypropyltriethoxysilane, aminopropyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, etc. A condensate of about 2 to 10 molecules can be exemplified.

  Further, in the present invention, in addition to the coating agent containing the compound of formula 1, in addition to the coating agent containing both the compound of formula 1 and the compound of formula 2, a coating agent to which the compound of formula 3 is further added By using it, it is possible to add new properties such as organic properties of the compound of formula 3 or increase the properties such as organic properties compared to membrane materials produced without using them. It is.

The compound of the formula 3 is a compound composed of 4 substituents, 2 of which are hydrolyzable substituents and the other 2 of which are non-hydrolyzable substituents. In Formula 3, R ₉ and R ₁₁ may be the same or different and each is a hydrogen atom, an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and R ₁₀ and R ₁₂ are epoxy groups in the molecule. Or it is a C1-C10 alkyl group, alkenyl group, or phenyl group which may contain the glycidyl group.

  Specific examples of the compound represented by Formula 3 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane. And a condensate of about 2 to 10 molecules thereof. In addition, the compound of Formula 3 may be two or more kinds of such monomers, and also when two or more molecules of condensate are used, it is two or more kinds of condensates of such monomers. Also good.

Adding either the compound of formula 2 or the compound of formula 3 to the coating agent as described above can increase the organicity of the coating film, but both the compound of formula 2 and formula 3 are added to the coating agent. In this case, the organic property of the coating film can be further improved, and as a result, the water repellency of the film material can be further improved.
The compound of formula 2 and / or the compound of formula 3 is generally added to the coating agent in a range where the total amount does not exceed 50% by weight relative to the compound represented by the above formula 1, which is the main component of the coating agent. It is preferable to do. When the total addition amount of both (compounds 2 to 3) exceeds this range, when the coating agent is applied to the fiber substrate, it does not bind well with the compound of formula 1 as the main component, and the coating film This is because the strength may be insufficient. Therefore, when the compound of Formula 2 and / or the compound of Formula 3 is actually added, it is assumed that the strength of the coat film is lowered depending on the addition amount, and referring to the examples of the present specification. It is preferable to make the addition to a minimum after clarifying the range of the addition amount that can achieve the object by conducting a preliminary production test.

The primary role of the non-hydrolyzable substituents (R ₈ , R ₁₀ , R ₁₂ ) in the compound of formula 2 and the compound of formula 3 is to give flexibility to the coat film. Since these are organic substitutions such as alkyl groups, they also serve to impart water repellency to the coating film at the same time. In general, the organic substituent increases as the number of carbon atoms increases, that is, the water repellency increases.However, if the carbon number is too large, distortion occurs in the coating film due to steric hindrance, which causes a decrease in film strength. Become. Therefore, the number of carbon atoms of the organic substituent and the type and amount of each monomer constituting the compound of Formula 2 and / or Formula 3 (including the condensate) are referred to the examples in this specification, etc. It is preferable to determine by performing a preliminary production test.

On the other hand, siloxane bonds with strong heat resistance and wear resistance are also so-called “hard” bonds. Because of this “hardness”, when applied to a fiber substrate such as a woven fabric, the substrate can be given abrasion resistance. However, fiber base materials such as woven fabrics are characterized by flexibility, and membrane materials are sometimes required to have flexibility similar to that of the fibers that are the materials.
Conventionally used sol / gel coating agents generally use tetraalkoxysilane [Si (OR) ₄ ] or an oligomer thereof as a starting material. When this is completely hydrolyzed [(1) to (3) in the following reaction formula 1] to form a coat film, all four bonds of silicon atoms form a network of hard siloxane bonds, and ceramic However, since it becomes a brittle film lacking flexibility, it is practically impossible to produce a film material utilizing flexibility such as fibers.
However, the present invention uses a compound of formula 1 in which one of the four substituents of the silicon atom is not hydrolyzed as a main component of the coating agent, and has good compatibility with the coating agent. This problem has been solved by selecting a resin that does not impair flexibility, and further optimizing the method of attaching the coating agent to the fiber base material and the resin.
In the present invention, the flexibility and the like can be further increased by adding the compound of formula 2 and the compound of formula 3 each having one or two substituents that are not hydrolyzed to the coating agent.

  As a catalyst for curing and solidifying the compound represented by the above formula 1 (including compounds 2 to 3, the same applies hereinafter), a commonly used catalyst can be used without any particular limitation. For example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid can be exemplified as an acid catalyst. Examples of the base catalyst include ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, ethanolamine, diethanolamine, and triethanolamine. When these ordinary catalysts are used, reaction water is allowed to coexist in order to cure and solidify the compound of Formula 1.

  The coating agent applied in the present invention thus contains the compound of formula 1 (including compounds 2 to 3), a catalyst, and reaction water. In normal use, there is no particular problem, but when it is stored for a long period of time, there is a problem that the coating agent is easily gelled by the reaction water. In order to solve this, it is preferable to use a hydrolyzable organometallic compound as a catalyst instead of the above-described ordinary catalyst. If a hydrolyzable organometallic compound is used, there is no need to coexist with reaction water, which is preferable for long-term storage stability.

When an organic metal compound is mixed with a compound of formula 1 (including compounds 2 to 3) to form a coating agent, and this is applied to a fiber substrate, moisture on the fiber or moisture in the air (humidity) is absorbed, and the organic metal Although the compound hydrolyzes itself, at this time, it forms a network with the compound of formula 1, and the compound of formula 1 (including compounds 2 to 3) is cured and solidified.
Examples of the organometallic compound preferably used in the present invention include those containing titanium, zirconium, aluminum or tin. More specifically, tetrapropoxy titanate, tetrabutoxy titanate, tetrapropoxy zirconate, tetrabutoxy zirconate, tripropoxy aluminate, aluminum acetylacetonate, dibutyltin diacetate, dibutyltin dilaurate and the like can be exemplified.

  The amount of the above catalyst (acid catalyst, base catalyst or organometallic compound) used is usually 1 to 30 parts by weight, preferably 100 parts by weight of the compound represented by formula 1 (including compounds 2 to 3). Is 4 to 10 parts by weight.

  In the present invention, an organic solvent may be added to the coating agent to be applied in order to uniformly mix the compound of formula 1 (including compounds 2 to 3), a catalyst, and optionally necessary reaction water. it can. Examples of the organic solvent used for this purpose include alcohols. More specifically, methanol, ethanol, propanol, isopropanol, butanol, pentanol or hexanol can be exemplified. In addition, the viscosity and drying speed of the coating agent can be adjusted by controlling the amount of addition.

For the purpose of such adjustment, in particular glycols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, methoxyethanol, propoxyethanol, butoxyethanol, methoxypropanol, ethoxypropanol, propoxypropanol Alternatively, it is preferable to use an organic solvent having a high viscosity or boiling point, such as cellosolve such as butoxypropanol, alone or in combination. Of course, the alcohols may be added simultaneously with one or more organic solvents having a high viscosity or boiling point. When the purpose is to adjust the viscosity and drying speed of the coating agent, the same effect can be achieved not only by the organic solvent but also by a surfactant.
In particular, the glycols and cellosolves described above have a hydroxyl group in the molecule and are therefore introduced into the network of siloxane bonds formed by the condensation reaction of the compounds of formula 1 (including compounds 2 to 3). Sometimes. Since glycols and cellsolves have organic properties, the introduction of them increases the organicity of the resulting coating film, that is, increases the organicity of the film material.

  The amount of the organic solvent used is such that the concentration of compound 1 (including compounds 2 to 3) in the coating agent used in the present invention (and the following other additives used as necessary) is usually 10 The amount is -80% by weight, preferably 20-60% by weight.

The coating agent of the present invention is blended with additives such as pigments, flame retardants, ultraviolet absorbers, plasticizers, lubricants, stabilizers, fillers, lubricants, curing agents, antifoaming agents, and antifungal agents. be able to.
These additives can be used alone or in combination of two or more.

The antifouling film material of the present invention may be (1) a fiber base material formed by forming a resin layer on both sides or one side, and the coating agent of the present invention applied on both sides or one side, or (2) What formed the resin layer on the both surfaces or single side | surface of the fiber base material which apply | coated the coating agent used for this invention on both surfaces or single side | surface may be used.
In the antifouling film material of the present invention, the fiber base material, the resin layer, and the coating agent are combined to form a composite in any of the above (1) or (2).

In the case of (1), a film material obtained by fixing a resin to a fiber base material is cut and processed into an arbitrary size and shape, and the above-described coating agent is applied thereto.
Here, the fiber base material used in the present invention includes natural fibers such as cotton and hemp, inorganic fibers such as glass fibers, carbon fibers and metal fibers, and synthetic fibers such as polyamide fibers, polyester fibers, It consists of at least one selected from aromatic polyamide fiber, acrylic fiber, polyvinyl chloride fiber, polyolefin fiber and the like.
Generally, the fiber used for the base fabric of the antifouling film material of the present invention is preferably a polyester fiber, and the single fiber fineness is preferably in the range of 0.1 to 10 dtex. Further, the fiber material in the base fabric may be any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn, etc., and the base fabric may be woven fabric, knitted fabric, non-woven fabric, or these Any of these composite fabrics may be used.
The basis weight of the fiber base material is preferably 1 to 500 g / m ^2.

In addition, the resin used in the present invention is not particularly limited, but a resin having excellent weather resistance is preferable. The resin excellent in weather resistance here means a resin excellent in yellowing resistance, color retention, gloss retention, chemical resistance and the like, and any of water-soluble type and solvent type can be used. For example, vinyl chloride resin, fluorine resin, polyolefin resin, polyester resin, silicon resin, urethane resin, acrylic resin, polyvinyl alcohol resin and the like are preferably used. In general, the resin used for the antifouling film material of the present invention is particularly preferably a vinyl chloride resin having good compatibility with the coating agent.
Forming the resin layer on the fiber substrate is not particularly limited, and examples thereof include known coating methods, topping methods, dipping methods, laminating methods, gravure methods, spraying methods, and the like (thickness of the resin layer). Can be adjusted according to the application.

A metal vapor deposition film or a metal foil may be bonded to the surface of the resin layer. In addition, such a membrane material is used to prevent water absorption on the fiber base fabric, to provide a plasticizer prevention layer to prevent bleedout of the plasticizer in the vinyl chloride resin, and to improve durability. Acrylic water repellent treatment or the like can be applied to the film material surface.
In the present invention, the fiber base material is prevented from bleeding out of the plasticizer in the vinyl chloride resin in order to further improve the weather resistance, for example, prior to the application of the coating agent. For this purpose, a vinyl fluoride film or the like may be laminated.

Application amount of the resin to the fiber base material, in terms of solid content basis weight, usually, 100~1,000g / m ^2, preferably from 400 to 800 / m ^2.

In the above (1), a specific method for applying the coating agent to the fiber substrate containing the resin is not particularly limited, and examples thereof include a known coating method, topping method, dipping method, laminating method, gravure method, and spraying method. The thickness of the coating layer can be adjusted depending on the application.
In addition, after apply | coating a coating agent, drying and heat processing are given, and this coating agent is hardened and solidified.
The drying and heat treatment conditions for curing and solidifying are usually a temperature of 30 to 250 ° C., preferably 120 to 230 ° C., a time of 1 to 30 minutes, and preferably 1 to 10 minutes.
The amount of the coating agent of the present invention applied to the fiber substrate is usually 0.1 to 10 g / m ² , preferably 1.0 to 5.0 g / m ² in terms of solid content basis weight.

As described above, when a coating agent is applied to a fiber base material containing a resin that has been or has not been subjected to a predetermined pretreatment, the compound of Formula 1 is hydrolyzed and (1) to (1) in the following Reaction Formula 1 Through the reaction shown in (3), a siloxane bond (Si—O—Si) is generated.
Reaction formula 1;
(1) Si—OR + H ₂ O → Si—OH + ROH
(2) Si—OH + HO—Si → Si—O—Si + H ₂ O
(3) Si—OH + RO—Si → Si—O—Si + ROH
The bond energy of Si—O in the siloxane bond (Si—O—Si) thus generated is 106 kcal / mol. On the other hand, the bond energy of the C—C bond, which is a typical bond of an organic compound, is 82.6 kcal / mol. Therefore, it can be seen that the vitreous coat film having a siloxane bond produced by hydrolysis of the compound of Formula 1 has a much more thermally stable bond than the organic compound. Due to this thermally stable bond, the coating film applied in the present invention has excellent heat resistance and wear resistance, and as a result, it is possible to produce a film material having excellent heat resistance and wear resistance. Become.

Further, when the coating agent applied in the present invention contains the above-described organometallic compound (for example, tetrabutoxytitanium) as a catalyst, the reaction formula 1 can be used even if the coating agent does not contain reaction water. Although the reactions (1) to (3) proceed, the reaction in this case is specifically as shown in (4) and (5) in the following reaction formula 2.
Reaction formula 2;
(4) Ti—OR + H ₂ O → Ti—OH + ROH
(5) Ti—OH + RO—Si → Ti—O—Si + ROH

  As described above, by introducing the Ti—O bond into the coat film, the heat resistance and the wear resistance can be further improved as compared with the coat film having only the siloxane bond. As described above, when an organometallic compound is used as a catalyst, not only the reaction water does not need to coexist, but also the heat resistance and wear resistance of the coating film are further improved. The wear resistance can be made even stronger.

On the other hand, in the case of the above (2), a resin layer is formed on both sides or one side of the fiber base material coated with the coating agent of the present invention on both sides or one side.
In this case, the film material in which the coating agent of the present invention is applied to both sides or one side of the fiber base material is cut and processed into an arbitrary size and shape to form the above-described resin layer. The coating agent and resin used here, the amount of adhesion (weight per unit area), the specific method of applying them to the fiber substrate, the drying and heat treatment conditions of the coating agent, and the like are the same as described above.

  As described above, in view of the fact that the present invention has conventionally impaired light transmittance and flexibility by coating a thermoplastic resin or the like on one or both sides of a fiber base material in order to impart antifouling properties. As a result of intensive studies, (1) a film material obtained by fixing a resin to a fiber substrate is coated with a silane coating agent, or (2) a resin is applied to a film material obtained by coating a fiber substrate with a silane coating agent. When fixed, the fiber substrate, resin layer, and silane coating agent were combined into a composite, and surprisingly, excellent antifouling properties, light transmission, flexibility, and abrasion resistance as a membrane material structure It has been clarified that it is a thing that demonstrates.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, an Example is only an example and does not limit this invention.
In the following examples, the test methods used for performance evaluation of the antifouling film material are as follows.

(1) Outdoor exposure test A sample was placed southward at an inclination angle of 30 degrees, and a continuous outdoor exposure test was conducted to visually evaluate the antifouling property and the occurrence of rain-stained soil.
(I) Antifouling property Using the initial sample as a reference, the color difference ΔE on the sample surface after 12 months of exposure was measured, and the antifouling property was evaluated in four stages as follows.
ΔE is 10 or less: ◎ (not dirty)
ΔE is more than 10 and 20 or less: ○ (slightly dirty)
ΔE is greater than 20 and less than or equal to 30: Δ (dirty)
ΔE exceeds 30: x (severely dirty)
(B) Rain streak stains The appearance of rain streak stains was visually determined in three stages as follows.
◎: No rain streak ○: Slight rain streak
×: Rain streak

(2) Surface friction strength The friction strength of the sample was measured according to the Japanese Industrial Standard JIS L109 Martindale method. However, the sample was subjected to 5,000 friction tests at a load of 9 kPa, and the surface condition was visually evaluated. This test was conducted on the assumption that the membrane material was dragged to the ground when handling the membrane material or the membrane material surface was rubbed during cleaning. The membrane material of the present invention was used for a tent sheet, a building construction sheet, an automobile. When used for hood sheets, flexible container sheets, signboard backlit sheets, tarpaulin sheets, etc., a strength of ○ or higher is required.
A: No hue change B: Slight change (white turbidity)
×: Hue change

(3) Light Transmittance The total light transmittance of the sample was measured with a “direct reading haze computer device” manufactured by Suga Test Instruments Co., Ltd. according to the Japanese Industrial Standard JIS K7105 light transmittance measuring method.

(4) Flexibility The flexibility of the sample was measured according to the Japanese Industrial Standard JIS L1096 45 ° cantilever method. This test was carried out as an index of ease of handling and folding when film materials represented by tents were processed into various forms.
When the membrane material of the present invention is used for a tent sheet, a building work sheet, an automotive hood sheet, a flexible container sheet, a signboard backlit sheet, a tarpaulin sheet, etc., flexibility of 5 cm or less is required. .

(5) Water repellency The water repellency of the sample was evaluated according to the Japanese Industrial Standard JIS L1092 water repellency test method, and the water repellency was evaluated in the following five stages.
First grade: The sample surface shows wetness.
Second grade: half of the sample surface shows wetness and small individual wetness penetrates the sample.
Third grade: A sample that shows small individual water droplets on the sample surface.
Fourth grade: A sample that does not get wet on the surface of the sample but shows adhesion of small water droplets.
Grade 5: No moisture or water droplets adhered to the sample surface.

Example 1
A plain woven fabric (warp density: 70 / inch, weft density 38 / inch) (weight per unit area of 110 g / cm ² as a fiber base material) was used as the fiber base fabric. This fiber base fabric is subjected to urethane treatment on the back surface (manufactured by Daiichi Seika Co., Ltd., hard yellowing ether urethane ME8105LP, basis weight = 20 g / m ² ), and then the surface of the fiber base fabric is coated with a coating agent [compound 14 g of methyltrimethoxysilane condensate (n = 3-4), 5.0 g of phenyltrimethoxysilane, 20.0 g of isopropyl alcohol as a solvent, and 0.8 g of tetrabutoxytitanium as a catalyst] First, drying was started from 60 ° C., the temperature was gradually raised, and finally the temperature was raised to 100 ° C. to apply and dry. At this time, the solid weight per unit area of the coating agent was about 2.5 g / m ² .

Example 2
A plain woven fabric (warp density: 38 pieces / inch, weft density 38 pieces / inch) (weight per unit area of the fiber substrate is 110 g / m ² ) of polyester fiber filaments (550 dtex / 96 filaments) was used as the fiber base fabric. A sheet in which a vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., straight PVC) was fixed to both sides of the base fabric by a doctor knife coating method was prepared. A plasticizer, a stabilizer, a flameproofing agent and a filler were added to the vinyl chloride resin, and the mixture was roughly kneaded with a butterfly mixer, further uniformly kneaded with a triaxial roll, and then adjusted with a solvent to adjust the viscosity. The basis weight of the resin layer was 550 g / m ² . The film material thus obtained was coated with a coating agent [methyltrimethoxysilane condensate (n = 3 to 4) 14 g, phenyltrimethoxysilane 5.0 g, isopropyl alcohol 20.0 g as a solvent, and catalyst as a catalyst. A mixture of 0.8 g of dibutyltin diacetate] was soaked for 30 seconds, drying was first started from 60 ° C., the temperature was gradually increased, and finally the temperature was increased to 100 ° C., followed by drying. At this time, the solid weight per unit area of the coating agent was about 3.0 g / m ² .

Comparative Example 1
The same composition fiber base fabric used in Example 1 was subjected to urethane processing on the back surface (manufactured by Dainichi Seika Co., Ltd., hard yellowing ether urethane ME8105LP, basis weight = 20 g / m ² ), and vinyl chloride resin A film material was prepared by adhering (straight PVC manufactured by Shin-Etsu Chemical Co., Ltd.) to the base fabric by a doctor knife coating method 550 g / m ² .

Comparative Example 2
A membrane material in which a fluororesin (manufactured by Asahi Glass Co., Ltd., Fullon) was fixed to the base fabric by the 500 g / m ² doctor knife coating method was prepared on the fiber base fabric having the same configuration used in Example 2. .

Comparative Example 3
A membrane material in which an acrylic resin (manufactured by Iupika Japan Co., Ltd., Iupica 4300) is fixed to the base fabric by the 520 g / m ² doctor knife coating method to the fiber base fabric having the same configuration used in Example 2. Produced.
Next, Table 1 shows the results of evaluation of antifouling property, rain stain, surface friction, and light transmittance by the above test.

From Table 1, according to the present invention, no rain streak was observed, it was resistant to surface friction, and further improved in light transmission, so that it was a problem in the conventional film material coated with a thermoplastic resin. Membranes for outdoor use can solve various problems such as adhesion of dirt due to increased adhesion due to migration of plasticizer to the surface of the membrane material, light transmission deterioration due to resin coating, and shortening of membrane material life due to surface abrasion during cleaning. Ideal as a material.
Next, the results of evaluating the flexibility and water repellency by the above test are shown in Table 2.

  From Table 2, the material according to the present invention is highly flexible and has a high water-repellent effect, so that sufficient antifouling properties can be secured, and is optimal as a film material for outdoor use.

The antifouling film material of the present invention is excellent in antifouling property due to the water repellent effect, and is also excellent in light transmission, flexibility, and wear resistance. It can be used for a wide range of applications such as tents, warehouse tents, signboards for signboards, backlits for signboards, hoods for automobiles, flexible containers, tarpaulins, etc., and enables multi-functionalization of membrane materials.

Claims (4)

A silane-based coating agent composed mainly of a fiber base material, a resin, and a compound represented by the following formula 1 is combined, and the silane-based coating agent is cured and solidified by the action of a catalyst. Antifouling film material.

(In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a number of 2 to 10)   The antifouling film material according to claim 1, wherein a coating agent is applied to both surfaces or one surface of a fiber base material formed by forming a resin layer on both surfaces or one surface.   The antifouling film material according to claim 1, wherein a resin layer is formed on both surfaces or one surface of a fiber base material coated with a coating agent on both surfaces or one surface. The fiber which comprises a fiber base material exists in the range of the single fiber fineness of 0.1-10 dtex, and the fabric weight of this fiber base material is 1-500 g / m < ² >, Any one of Claims 1-3. Antifouling film material.