JPH1177921A - Vinyl chloride resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce adhesion of films with each other during operation by applying a curing composition having a vinyl polymer as a principal chain, and consisting of a silicon modified polymer including a hydroly zable silyl group, a polysiloxane group, and hydroxyl group in side chains, a curing agent and/or curing catalyst. SOLUTION: A curable composition is prepared by mixing a silicon modified vinyl polymer having a vinyl polymer as a principal chain and including hydrolytic silyl group and polysiloxane group, and hydroxyl group in side chains, and a curing agent and/or curing catalyst. The curable composite is applied on a vinyl chloride resin film, and the solvent is volatilized by heating, thus forming a coating film on the vinyl chloride resin film through crosslinking hardness by a condensation reaction of the hydrolytic silyl group existing at the side chains by a curing catalyst on the film, crosslinking hardening by additional reaction with a curing agent such as multivalent isocyanate and the hydroxyl group existing at the side chains, or crosslinking hardening by both the reactions thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-coated vinyl chloride resin film. More specifically, the present invention relates to a vinyl chloride resin film for agricultural use in which films do not stick to each other and have improved dustproofness.

[0002]

2. Description of the Related Art Agricultural soft vinyl chloride resin films contain a large amount of a plasticizer, and the plasticizer bleeds out to the surface during use to reduce dust resistance. The adhering dust reduces the transparency of the film, thereby deteriorating the light transmittance and affecting the growth of the crop. Therefore, there is a demand for a film having good dust resistance and maintaining the transparency of the film for a long period of time. In order to maintain these properties for a long period of time, coated PVC films in which a film is coated with a coating agent have been developed.

[0003]

However, a PVC film coated with such a coating agent has a problem that the coated surface becomes sticky, sticky, and sticks on the surfaces where the films are in contact with each other, thereby reducing workability. Is in question. Especially in the summer, when the film is rolled up and stretched while the coated film is being stretched, the films stick together, causing a major problem such as failure of the automatic opening / closing device and long time required for the opening / closing operation. . A film coated with a silicone-modified vinyl resin has been proposed as a vinyl chloride resin film having improved non-adhesiveness and dustproof properties between the films (Japanese Patent Application Laid-Open No. 4-135749). However, this coated film was still insufficient in terms of non-adhesive performance and dust resistance. The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and have reached the present invention.

That is, the present invention has solved the above-mentioned problems by the following constitution. (1) A curable composition comprising a silicone-modified vinyl polymer having a main chain of a vinyl polymer and having a hydrolyzable silyl group, a polysiloxane group, and a hydroxyl group in a side chain, and a curing agent and / or a curing catalyst. PVC resin film coated with an object. (2) The silicone-modified vinyl polymer is a vinyl group-containing alkoxysilane vinyl group-containing polysiloxane
The curable composition according to item (1), which is obtained by copolymerizing a vinyl compound having a hydroxyl group and another polymerizable vinyl compound in at least one alcohol solvent. Vinyl chloride resin film applied. (3) vinyl group-containing alkoxysilane vinyl group-containing polysiloxane vinyl compound having a hydroxyl group,
And a vinyl chloride resin film coated with the curable composition according to item (2), wherein all of the other polymerizable vinyl compounds are acrylates or methacrylates. (4) A vinyl chloride resin film coated with the curable composition according to (1) or (2), wherein the curing agent is a polyvalent isocyanate compound. (5) A vinyl chloride resin film coated with the curable composition according to (1) or (2), wherein the curing catalyst is an organometallic compound. (6) A vinyl chloride resin film coated with the curable composition according to (1) or (2), wherein the curing agent is a polyisocyanate and / or a blocked isocyanate comprising isophorone diisocyanate. (7) A vinyl chloride resin film coated with the curable composition according to (1) or (2), wherein the curing catalyst is an organotin compound.

[0004]

Next, the present invention will be described in detail.
The summary of the present invention is to blend a silicone-modified vinyl polymer having a main chain of a vinyl polymer and having hydrolyzable silyl groups, polysiloxane groups and hydroxyl groups in side chains, and a curing agent and / or a curing catalyst. The curable composition is applied to a vinyl chloride resin film, the solvent is volatilized by heating, and the film is cured by a curing catalyst to form a cross-linking cure by a condensation reaction of hydrolyzable silyl groups present in side chains, or a polyvalent isocyanate. The cross-linking and curing by the addition reaction of the above-mentioned curing agent with the hydroxyl group present in the side chain, or the cross-linking and curing by both of these reactions forms a coating film on the film.

The silicone-modified vinyl polymer used in the present invention contains 1 to 25% by weight of a vinyl group-containing silane compound, 0.1 to 20% by weight of a vinyl group-containing polysiloxane, and 10 to 30% by weight of a hydroxyl group. The vinyl compound contained can be obtained by addition polymerization of a vinyl group in a solvent such as alcohol with 25 to 90% by weight of a monomer of another polymerizable vinyl compound. In a curable composition in which the polymerization reaction product and a curing agent are dissolved in a solvent,
There was concern about the consumption of isocyanate groups due to the reaction between the hydroxyl groups in the alcohol that is the solvent and the polyvalent isocyanate compound used as the curing agent, but surprisingly, the curable composition used in the present invention has poor curing. Similarly, the finding that the non-adhesive performance and dustproofness of the coated film are good is one of the factors for completing the present invention. Alcohols are generally inexpensive general-purpose solvents and, unlike other organic solvents, do not attack the surface of the vinyl chloride resin film. Further, during polymerization or storage, there is a mutual interaction between hydrolyzable silyl groups present in the polymer. This is because there is an effect of suppressing the increase in the molecular weight of the silicone-modified vinyl polymer due to the condensation reaction.

The details of the silicone-modified vinyl polymer will be described below. The vinyl group-containing silane compound, which is one of the copolymerized components of the silicone-modified vinyl polymer, has one to three hydrolyzable functional groups directly bonded to a silicon atom other than a vinyl group, These functional groups are not particularly limited, but an alkoxy group having 1 to 4 carbon atoms and an acetoxy group are easily used, and preferable results are obtained. Specific examples of such a vinyl monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, methylvinyldimethoxysilane, and γ-acryloxypropyl. Trimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltriacetoxysilane and styrylethyltrimethoxysilane. Among them, γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane are preferred.

The hydrolyzable silyl group introduced into the side chain of the vinyl polymer is hydrolyzed by moisture in the air to become an active silanol group, and the silanol groups are silanol groups and / or alkoxysilyl groups. It can be used as a cross-linking component of a resin to cause a condensation reaction with a hydrolyzable silyl group such as a group. Further, the siloxane bond formed by this cross-linking reaction has a high binding energy and thus has excellent weather resistance. At least one of the above silane compounds is used, and the use ratio is preferably 1 to 25% by weight of all monomers. If the amount is less than 1% by weight, the obtained coating film cannot be said to have sufficient adhesion to the PVC film, and the use ratio is 25%.
If the amount is more than 10% by weight, the resulting coating tends to be brittle. As the vinyl group-containing polysiloxane, the following general formula

[0008]

Embedded image And a specific example of R ¹ is

[0009]

Embedded image

R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is each independently a methyl group or a phenyl group, m is an integer of 1 to 3, and n is an integer of 0 to 1500. One terminal vinyl group-containing polysiloxane shown, or the following general formula,

[0011]

Embedded image

Wherein R ¹ , R ³ and n are the same as defined above and include polysiloxanes containing vinyl groups at both ends. Specific examples of the vinyl group-containing polysiloxane include vinyldimethylpolysiloxane at one end or both ends, methacryloxypropyldimethylpolysiloxane at one end or both ends, tris (trimethylsiloxy) silylpropyl methacrylate, and the like. The viscosity range of these polysiloxanes is 3 to 1000 (10-3 Pa.s).
The degree is preferred. Weight average molecular weight is 200 to 10000
It is preferably in the range of 0. The vinyl group-containing polysiloxane is used in an amount of 0.1 to 0.1% of all monomers used for polymerization.
It is preferably 20% by weight, and in some cases, two or more vinyl group-containing polysiloxanes may be used in combination. By incorporating a polysiloxane chain into the side chain of the vinyl polymer, water repellency, slipperiness, releasability, flexibility and the like can be imparted.

Examples of the hydroxyl-containing vinyl compound include 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, polyethylene glycol methacrylate, glycerol methacrylate, and the like, and methacrylates containing a hydroxyl group, 2-hydroxyethyl acrylate. 2-hydroxybutyl acrylate, polypropylene glycol acrylate, 2-hydroxy-3 acrylate
Acrylates such as phenyloxypropyl,
And vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether. Of these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred. At least one kind of these hydroxyl group-containing vinyl compounds is used, and the use ratio is preferably 10 to 30% by weight of the total monomers.

Other polymerizable vinyl compounds include:
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, acrylates such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, lauryl methacrylate, stearyl methacrylate Methacrylates such as styrene, α-methylstyrene, styrenes such as chloromethylstyrene, methyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as cyclohexyl vinyl ether, vinyl acetate, vinyl such as vinyl benzoate Esters, vinyl fluoride, vinylidene fluoride,
Trifluoroethylene, chlorotrifluoroethylene,
Fluoroolefins such as fluoroalkyltrifluoroethylene, ethylene, propylene, and other olefins such as vinyl chloride, carboxylic acid-containing vinyl compounds, acrylic acid, methacrylic acid, maleic acid,
Examples include itaconic acid and maleic anhydride, which is an acid anhydride. By adding and polymerizing a carboxylic acid group-containing vinyl monomer, the adhesion of the resulting curable resin, the compatibility when blending resins other than the silicone-modified vinyl resin, and the dispersibility of inorganic fillers such as pigments are improved. Can be achieved. In addition, when a vinyl monomer containing an epoxy group is used among the vinyl monomers, the functional group can be thermally crosslinked by heating.
The use ratio of this carboxylic acid group-containing vinyl monomer is preferably 5% by weight of all monomers. The above-mentioned other monomer of the essential component can be used alone, but it is preferable to use two or more kinds in combination.
As for the use ratio, 25 to 90% by weight of the total monomer is used, and more preferably, 50 to 80% by weight is used.

As described above, the reaction solvent has a carbon number of 1 to 6 in order to suppress a high polymer at the time of polymerization, to improve the storage stability of the obtained polymer and to prevent swelling of the vinyl chloride resin film to be coated. It is preferable to use at least one or more alcohols. Such alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, 2-methyl-2-propanol,
1-pentanol, 3-pentanol, 4-methyl-2
Alkyl alcohols such as pentanol, 1-hexanol, cyclohexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethyl carbitol, 3-methoxybutanol,
Ether alcohols such as -methyl-3-methoxybutanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Of these, isopropanol and propylene glycol monomethyl ether are preferred. Furthermore, after the completion of the polymerization reaction, such a solvent may be used to dilute the mixture to an appropriate viscosity in order to make the viscosity suitable for coating.

Further, in order to dissolve the polymerization initiator described below and improve the appearance of the coating film, hydrocarbons such as toluene, xylene, n-hexane and cyclohexane, and acetates such as ethyl acetate and butyl acetate. , Ethers such as cellosolve acetate, propylene glycol methyl ether acetate, acetone,
Ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone, and diacetone alcohol can be used alone or in combination of two or more at the time of reaction and dilution.

Solution polymerization is preferred as the polymerization method for obtaining the silicone-modified vinyl polymer of the present invention. That is, in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, the above-described solvent is charged, and preferably, a mixture of each of the above monomers at a temperature of 50 to 150 ° C. and a polymerization initiator are added. The reaction is carried out by gradually dropping from the dropping tank into the reaction vessel. A dropping time of about 2 to 6 hours is practically preferable. After dropping,
In order to polymerize the unreacted monomer, the heating may be continued for several hours at the same temperature as that at the time of dropping or by raising the reaction temperature, and a polymerization initiator may be additionally supplemented. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, t-butylperoxyoctoate, and t-butylperoxybenzoate, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile. It can be suitably used.

The degree of polymerization of the resulting silicone-modified vinyl polymer is from 5000 to 15 in terms of weight average molecular weight.
0000 is preferable. The degree of polymerization can be adjusted by the kind and amount of the radical generator, the polymerization temperature and the use of the chain transfer agent. As the chain transfer agent, n
-Dodecyl mercaptan, t-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane and the like can be suitably used. If the weight average molecular weight is less than 5000, unpolymerized monomers tend to remain, which is not preferable. On the other hand, when the weight average molecular weight exceeds 150,000, defects such as stringing often occur during coating.

Various additives may be further added to the silicone-modified vinyl polymer used in the present invention, if necessary. Additives include dispersants, defoamers, thickeners, anti-settling agents, anti-sag agents, leveling agents, matting agents, abrasion inhibitors, ultraviolet absorbers, light stabilizers, antioxidants, antibacterial agents, etc. Is mentioned. As described above, the silicone-modified vinyl polymer used in the curable resin composition can be obtained.

As the curing agent of the present invention, any curing agent capable of cross-linking the hydroxyl groups introduced into the side chains of the silicone-modified vinyl polymer can be suitably used. Examples of such a curing agent include a polyvalent isocyanate compound and a melamine compound. Among them, it is preferable to use a polyvalent isocyanate compound from the viewpoint of reactivity and weather resistance of the obtained film. Specific examples of such polyvalent isocyanate compounds include aliphatic xylene diisocyanate,
Isophorone diisocyanate, hexamethylene diisocyanate or their polyhydric alcohol addition type,
Bullet type, trimer type, aromatic tolylene diisocyanate, polyvalent isocyanate compounds such as diphenylmethane diisocyanate, and blocked isocyanate compounds in which a reactive group is protected with a blocking agent so that a coating agent can be used in a one-pack type. .

Among these, an isophorone diisocyanate compound and a polyisocyanate and a blocked isocyanate comprising the same are particularly preferred from the viewpoints of the drying property of the coating agent and the hardness of the obtained film. Representative commercially available polyisocyanate compounds include Takenate D-110N, D-140N, and D-16N manufactured by Takeda Pharmaceutical Company Limited.
0N, D-165N90CX, D-170N, D-18
0N, D-102, D-202 "and" Coronate EH, HL, L "manufactured by Nippon Polyurethane Industry Co., Ltd. As a commercially available block isocyanate compound, Taketake B-815 manufactured by Takeda Pharmaceutical Co., Ltd. is available.
N, B-820NSU, B-842N, B-846N,
B-870N "and" Coronate 2507, 2515 "manufactured by Nippon Polyurethane Industry Co., Ltd. These can be used alone or in combination of two or more. Further, it may be used by diluting it with an organic solvent excluding alcohols so as to have an appropriate viscosity, or may be used in combination with a curing catalyst described later.

The use ratio of the silicone-modified vinyl polymer and the polyvalent isocyanate compound can be represented by the ratio of OH group / NCO group, and the respective amounts used are the hydroxyl value of the silicone-modified vinyl polymer and the polyvalent isocyanate compound. Can be calculated by a known and commonly used method from the NCO content. For example, when OH / NCO = 1/1 (molar ratio), the required amount of the polyvalent isocyanate compound per 100 g of the silicone-modified vinyl polymer is represented by (OH value / NCO content (% by weight)) × 7.49. Is done. In the curable resin composition of the present invention, the OH / NCO ratio of the silicone-modified vinyl polymer and the polyisocyanate compound, which is a kind of polyvalent isocyanate compound, is 1 / (0.05 to 0.1.
5 (molar ratio)) is preferable. If the NCO is less than 0.05, the performance of the obtained coated film cannot be said to be sufficient, and if it exceeds 0.5, the coating tends to be brittle.

The curing catalyst of the present invention is used as a condensation catalyst when the alkoxysilyl groups introduced into the side chains of the silicone-modified vinyl polymer are crosslinked by the influence of moisture in the air. Examples of the curing catalyst of the present invention include organometallic compounds, amine compounds and acidic compounds.

Specific examples of the organometallic compound include tin octylate, di-n-butyltin dioctate, di-n-butyltin dilaurate, di-n-octyltin bis (isooctylthioglycolate), di-n Organic tin compounds such as -butyltin sulfide, di-n-octyltin oxide, zinc octenoate, magnesium naphthenate or tetraisopropoxytitanium, tetra-n-butoxytitanium, isopropyltriisostearoyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Examples thereof include organic titanium compounds such as titanate, and organic aluminum compounds such as aluminum isopropylate and aluminum tris (acetylacetonate). Examples of the amine compound include triethylamine, ethylenediamine, diethylenetriamine, dimethylaminoethanol, and isophoronediamine. Examples of the acidic compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, phthalic acid, phthalic anhydride, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, and organic amine block compounds thereof. Of these, organometallic compounds are preferred from the viewpoint of reactivity, and organotin compounds are particularly preferred from the viewpoint of the performance of the resulting coated film.

These curing catalysts can be used alone or in combination of two or more as necessary. The amount used is
The amount is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the solid content of the silicone-modified vinyl polymer. When the amount added is 0.
If the amount is less than 01 parts by weight, the performance of the coated film cannot be said to be sufficient. If the amount is more than 2 parts by weight, the curing strain generated at the time of curing becomes large and the film tends to become brittle.

A hydrolyzable ester can be added to the silicone-modified vinyl polymer and the curing agent of the present invention as a dehydrating agent. By adding a hydrolyzable ester, water in the system can be removed and the storage stability can be further improved. Examples of the hydrolyzable ester in this case include dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane, 1,1-dimethoxycyclohexane, methyl orthoformate, ethyl orthoformate, Methyl orthoacetate, ethyl orthoacetate, dimethyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-
Examples include aminopropyltriethoxysilane, methyl silicate, and ethyl silicate. The amount of the hydrolyzable ester used is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the silicone-modified vinyl polymer and the curing agent, respectively.

The vinyl chloride resin used as the base material of the film of the present invention is a vinyl chloride homopolymer or a vinyl resin containing vinyl chloride as a main component, wherein vinyl chloride and another copolymerizable monomer, for example, Copolymers such as vinyl acetate, vinylidene chloride, (meth) acrylate, ethylene, and propylene can also be used. These are polymerized by known and common polymerization methods (emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc.), and the average degree of polymerization is 10
00 to 2000 is preferred. Various additives may be added to the thus obtained vinyl chloride resin as needed, for example, a plasticizer, a lubricant, a heat stabilizer, an anti-fogging agent, an anti-fog agent, a warming agent, an antistatic agent, an ultraviolet absorber, Pigments, dyes and the like may be added.

Suitable plasticizers to be used include di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate,
Phthalic acid derivatives such as didodecyl phthalate and diundecyl phthalate; adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate; maleic acid derivatives such as di-n-butyl maleate; and citric acid such as tri-n-butyl citrate Derivatives, itaconic acid derivatives such as monobutyl itaconate, oleic acid derivatives such as butyl oleate, tricresyl phosphate, epoxidized soybean oil, and epoxy resin plasticizer. Suitable lubricants, heat stabilizers, polyethylene wax, bisamide, stearic acid, zinc stearate, barium stearate, calcium stearate,
And barium ricinoleate. Examples of the ultraviolet absorber include benzotriazole, benzoate, benzophenone, cyanoacrylate, and phenyl salicylate ultraviolet absorbers. Examples of pigments and dyes include titanium oxide, silica, ultramarine, and phthalocyanine blue.

These are mixed by a usual blending technique and mixing technique, for example, a ribbon blender, a Banbury mixer, a super mixer and other blending machines and mixers, and then formed into a film by a calendar method, an inflation method, a T-die method, or the like. A vinyl chloride resin film can be obtained. When the thickness of the film is too thin, the strength is insufficient and it is not preferable. On the contrary, when the thickness is too thick, workability such as house expansion is hindered.
mm.

In applying the curable composition of the present invention, any of a roll coater method, a blade coater method, a gravure coater method, a beat coater method, a curtain flow coater method and a spray coating method may be used. It can be applied to one or both sides of the film.
After application, when curing, it can be cured at any temperature from room temperature to 150 ° C., but at a temperature of 60 to 120 ° C. for 10 seconds to 10 seconds.
It is preferable to heat and dry for minutes.

The thickness of the coating film of the curable resin composition of the present invention is preferably from 0.1 to 5 μm. If the thickness is less than 0.1 μm, the dust resistance is not sufficient. Conversely, if it exceeds 5 μm,
When processing the film, cracks and peeling are likely to occur in the coating, which is not preferable. As described above, the coated vinyl chloride resin film according to the present invention is obtained.

[0032]

EXAMPLES Hereinafter, the present invention will be described specifically and in detail with reference to examples, but the present invention is not limited to the examples. (Synthesis of Silicone-Modified Vinyl Resin) 100 parts by weight of isopropyl alcohol was charged into a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
Heated to ° C. Under stirring and nitrogen atmosphere, 40 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl methacrylate, 18 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of n-butyl acrylate, γ-methacryloxypropyltrimethoxysilane 5 Parts by weight, methacryloxypropyldimethylpolysiloxane at one end (weight average molecular weight 550)
0) A mixture of 1 part by weight, 1 part by weight of methacrylic acid and 1 part by weight of azobisisobutyronitrile was added dropwise over 4 hours. Further, 1 part by weight of azobisisobutyronitrile was dissolved in and added to 20 parts by weight of ethyl acetate, and the reaction was continued at the same temperature for 4 hours to obtain a silicone-modified vinyl polymer having a weight average molecular weight of 60000. 200 parts by weight of isopropyl alcohol and 80 parts by weight of ethyl acetate were added to this resin solution to prepare a solid content concentration of 20% by weight. (Hydroxyl value 16mg / g)

(Preparation of film) 100 parts by weight of vinyl chloride resin (average degree of polymerization: 1300), 45 parts by weight of dioctyl phthalate, 3 parts by weight of tricresyl phosphate, 3 parts by weight of epoxy resin, barium zinc stearate stabilizer A mixture of 3 parts by weight, 3 parts by weight of an antifogging agent and 0.1 part by weight of an ultraviolet absorber was kneaded at 160 to 170 ° C., and a 0.075 mm-thick vinyl chloride resin film was produced by a calender method.

Example 1 Takeda D-140N (NCO content: 10.8% by weight) manufactured by Takeda Pharmaceutical Co., Ltd. was added to 100 parts of a silicone-modified vinyl resin.
(OH / NCO = 1 / 0.36), coated by gravure coating, and dried at 100 ° C. for 2 minutes to prepare a coated film having a dry film thickness of 1 μm.

Example 2 100 parts of a silicone-modified vinyl resin was mixed with 0.1 part (0.5% by weight based on solid content) of di-n-butyltin dilaurate, and coated with gravure coat.
The coating film was dried at 0 ° C. for 2 minutes to prepare a coating film having a dry film thickness of 1 μm.

Example 3 Takeda D-140N (NCO content: 10.8% by weight) manufactured by Takeda Pharmaceutical Co., Ltd. was added to 100 parts of the silicone-modified vinyl resin.
Parts (OH / NCO = 1 / 0.18) and 0.02 parts of di-n-butyltin dilaurate (0.1
Wt%), paint with gravure coat,
The coating was dried at 00 ° C. for 2 minutes to prepare a coating film having a dry film thickness of 1 μm.

Comparative Example A silicone-modified vinyl resin was coated by gravure coating and dried at 100 ° C. for 2 minutes to produce a coated film having a dry film thickness of 1 μm. The following evaluation was performed about the coating film of Examples 1-3 and the comparative example. Table 1 shows the results
It was shown to.

[0038]

[Table 1]

(Stickness) The stickiness test was carried out according to JIS K6732. The compression bonding of the film was performed by two methods in which the coated surface (front surface) and the coated surface (front surface), and the coated surface (front surface) and the uncoated surface (back surface) were bonded together.

(Dustproof) The coated film was treated for 8 months.
The illuminance was measured by outdoor expansion in Sakurajima-cho, Kagoshima Prefecture, and using Topcon IM-20 manufactured by Tokyo Kogaku Co., Ltd. in the expanded state. The illuminance is the illuminance at the bottom of the coating film / illuminance at the open area ×
Expressed as 100 (%).

[0041]

As described above, the vinyl chloride resin film coated with the curable composition of the present invention has a low problem of adhesion between the films during the work due to the tackiness of the coated PVC film for agriculture, which has been a problem in the past, and is dustproof. The properties are also improved. Therefore, it is useful as an agricultural film requiring workability and transparency.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08F 290/06 C08F 290/06 C08L 27/06 C08L 27/06

Claims (7)

[Claims] 1. A curing method comprising a silicone-modified vinyl polymer having a main chain of a vinyl polymer and having a hydrolyzable silyl group, a polysiloxane group and a hydroxyl group in a side chain, and a curing agent and / or a curing catalyst. Vinyl chloride resin film coated with a hydrophilic composition. 2. The silicone-modified vinyl polymer is obtained by copolymerizing a vinyl group-containing alkoxysilane, a vinyl group-containing polysiloxane, a hydroxyl-containing vinyl compound, and another polymerizable vinyl compound in at least one alcohol solvent. 2. A vinyl chloride resin film coated with the curable composition according to claim 1, wherein the curable composition is applied. 3. A vinyl group-containing alkoxysilane, a vinyl group-containing polysiloxane, a vinyl compound having a hydroxyl group, and all other polymerizable vinyl compounds,
A vinyl chloride resin film coated with the curable composition according to claim 2, which is an acrylic ester or a methacrylic ester. 4. A vinyl chloride resin film coated with the curable composition according to claim 1, wherein the curing agent is a polyvalent isocyanate compound. 5. A vinyl chloride resin film coated with the curable composition according to claim 1, wherein the curing catalyst is an organometallic compound. 6. A vinyl chloride resin film coated with the curable composition according to claim 1, wherein the curing agent is a polyisocyanate and / or a blocked isocyanate comprising isophorone diisocyanate. 7. A vinyl chloride resin film coated with the curable composition according to claim 1, wherein the curing catalyst is an organotin compound.