JP2002161158A - Polyester resin building materials - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin building material excellent in transparency, which has a long-lasting ultraviolet absorbing ability over a long period of time and is hardly deteriorated in antifouling property of a film surface. SOLUTION: This is a polyester resin building material on which a coating made of an ultraviolet absorber is formed, wherein the ultraviolet absorber is:
A UV-absorbing monomer comprising a compound in which a 2-hydroxybenzophenone derivative is bonded as a side chain to a main chain of a vinyl compound, or at least one of a UV-absorbing monomer in which a 2-hydroxybenzotriazole derivative is bonded as a side chain to a main chain of a vinyl compound; A monomer mixture containing the ultraviolet absorbing monomer and a silicone macromer having a specific structure capable of being copolymerized contains a polymerized ultraviolet absorbing polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an agricultural film,
The present invention relates to a polyester resin building material such as a decorative sheet.

[0002]

2. Description of the Related Art Polyester resins are formed into various molded products, films, sheets and the like, and are used in many fields. For example, a greenhouse for cultivating agricultural crops usually has a structure in which a resin film is covered on a frame made of metal pipes. Conventionally, resin films include vinyl chloride resin and polypropylene resin. In addition, polyester resins are used. However, films made of vinyl chloride resin or polypropylene resin
Although it is inexpensive, its mechanical strength and weather resistance are not enough,
Applications are limited and are usually used in short-term houses and small houses within a few years. On the other hand, polyester resin films are more excellent in mechanical strength and weather resistance than these films, and thus are often used for long-term houses or large-sized houses that are used continuously for about 3 to 5 years. Polytester resins having more excellent weather resistance and strength have been used for building materials such as building sheets (decorative sheets). In these polyester resin films and sheets, low molecular ultraviolet absorbers such as benzotriazole-based and benzophenone-based are usually used in order to further improve the weather resistance.

[0003] As a method of using an ultraviolet absorber in a polyester resin film, a method of kneading the ultraviolet absorber into the resin at the time of extrusion molding of the film, or a method of applying the ultraviolet absorber to the formed film and applying the ultraviolet absorber to the film. Is formed on the film surface. However, in the method of kneading the ultraviolet absorber into the resin, the ultraviolet absorber may be heated during the kneading and sublimated. For this reason, there are increasing methods of forming a film of an ultraviolet absorber on the film surface.

[0004]

However, even when a film of an ultraviolet absorbent is formed on the surface of a film or sheet made of a polyester resin, the low molecular ultraviolet absorbent gradually bleeds out (dissolves), and the In some cases, it could not be used.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyester resin building material excellent in transparency, which has a long-lasting ultraviolet absorbing ability and hardly deteriorates the antifouling property of a film surface. Aim.

[0006]

The polyester resin building material of the present invention is a polyester resin building material on which a coating made of an ultraviolet absorber is formed, wherein the ultraviolet absorber has the following general formula (1) and / or Contains an ultraviolet absorbing polymer obtained by polymerizing a monomer mixture containing an ultraviolet absorbing monomer represented by (2) and a silicone macromer represented by the following general formula (3) copolymerizable with the ultraviolet absorbing monomer: It is characterized by doing.

Embedded image (In Formula 1, R ₁ represents any _one of hydrogen, an alkyl group having 1 to 6 carbon atoms, or an oxyalkyl group, and R ₂ represents an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group, or an absent. If R ₂ is absent, then X
Is directly bonded to the benzene ring. X represents any of an ester bond, an amide bond, an ether bond and a urethane bond. R ₃ represents hydrogen or a lower alkyl group. )

Embedded image (In the formula 2, R ₄ represents any one of hydrogen, halogen, and methyl group, R ₅ represents hydrogen or a hydrocarbon group having 1 to ₆ carbon atoms, R ₆ represents an alkylene group having 1 to 10 carbon atoms, R represents either an oxyalkylene group or absent.
_{When 6} indicates absent, Y is directly bonded to the benzene ring. Y represents an ester bond, an amide bond, an ether bond or a urethane bond. R ₇ has 1 to 8 carbon atoms
Represents an alkylene group, an aminoalkylene group, an alkyl group having a hydroxyl group in a side chain, or absent.
When R ₇ is absent, Y and C are bonded directly. R ₈ represents hydrogen or a lower alkyl group. )

Embedded image (In the formula 3, R ₉ represents hydrogen or a methyl group, R ₁₀ represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group, or absent. When R ₁₀ represents absent,
And Z are directly bonded. Z represents an ester bond or an amide bond. R ₁₁ represents an alkylene group having 1 to 6 carbon atoms, an aminoalkylene group, an alkyl group having a hydroxyl group in a side chain, or absent. When R ₁₁ is absent, Z and Si are directly bonded. N is an integer of 10 to 200. The monomer mixture preferably further contains a polymerizable vinyl compound copolymerizable with an ultraviolet absorbing monomer and a silicone macromer. The polymerizable vinyl compound,
It is preferable to include a polymerizable vinyl compound having active hydrogen. It is preferable that the ultraviolet absorber further includes a polyisocyanate-based crosslinking agent. The molecular weight of the ultraviolet absorbing polymer is preferably 10,000 to 300,000.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyester resin building material of the present invention has a structure in which an ultraviolet absorber is applied to the surface of a building material such as a film, a sheet, and a plate made of polyester such as polyethylene terephthalate and polybutylene terephthalate to form a coating. The ultraviolet absorbing agent used in the present invention contains an ultraviolet absorbing polymer, and the ultraviolet absorbing polymer includes an ultraviolet absorbing monomer represented by the following general formula (1) and / or (2), A monomer mixture containing a monomer and a copolymerizable silicone macromer represented by the following general formula (3) is polymerized.

[0008]

Embedded image (In Formula 1, R ₁ represents any _one of hydrogen, an alkyl group having 1 to 6 carbon atoms, or an oxyalkyl group, and R ₂ represents an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group, or an absent. If R ₂ is absent, then X
Is directly bonded to the benzene ring. X represents any of an ester bond, an amide bond, an ether bond and a urethane bond. R ₃ represents hydrogen or a lower alkyl group. )

[0009]

Embedded image (In the formula 2, R ₄ represents any one of hydrogen, halogen, and methyl group, R ₅ represents hydrogen or a hydrocarbon group having 1 to ₆ carbon atoms, R ₆ represents an alkylene group having 1 to 10 carbon atoms, R represents either an oxyalkylene group or absent.
_{When 6} indicates absent, Y is directly bonded to the benzene ring. Y represents an ester bond, an amide bond, an ether bond or a urethane bond. R ₇ has 1 to 8 carbon atoms
Represents an alkylene group, an aminoalkylene group, an alkyl group having a hydroxyl group in a side chain, or absent.
When R ₇ is absent, Y and C are bonded directly. R ₈ represents hydrogen or a lower alkyl group. )

[0010]

Embedded image (In the formula 3, R ₉ represents hydrogen or a methyl group, R ₁₀ represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group, or absent. When R ₁₀ represents absent,
And Z are directly bonded. Z represents an ester bond or an amide bond. R ₁₁ represents an alkylene group having 1 to 6 carbon atoms, an aminoalkylene group, an alkyl group having a hydroxyl group in a side chain, or absent. When R ₁₁ is absent, Z and Si are directly bonded. N is an integer of 10 to 200. )

The ultraviolet-absorbing monomer represented by the above general formula (1) is a compound in which a 2-hydroxybenzophenone derivative is bonded as a side chain to the main chain of a vinyl compound. For example, -BP-R-OH (BP : A compound having a functional group such as 2-hydroxybenzophenone skeleton) and -CH
= A compound in which a polymerizable vinyl compound having a functional group such as CR-COOH reacts and is bonded by an ester bond. Specific examples of such a monomer include 2-hydroxy-4-acryloyloxybenzophenone,
Hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- (2-acryloyloxy)
Ethoxybenzophenone, 2-hydroxy-4- (2-
Methacryloyloxy) ethoxybenzophenone, 2-
And hydroxy-4- (2-methyl-2-acryloyloxy) ethoxybenzophenone.

The ultraviolet absorbing monomer represented by the general formula (2) is a compound in which a 2-hydroxybenzotriazole derivative is bonded as a side chain to the main chain of a vinyl compound. Specific examples of such a monomer include 2- [2 ′
-Hydroxy-5 '-(methacryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-
5 '-(acryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-
5 '-(methacryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-3'-methyl-
5 '-(acryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -5-chlorobenzotritriazole, 2- [2'-hydroxy-5 '-( (Methacryloyloxyethyl) phenyl] benzotriazole, 2- [2′-hydroxy-5 ′-(acryloyloxyethyl) phenyl] benzotriazole, 2-
[2'-hydroxy-3'-t-butyl-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'-methyl-5'-
(Acryloyloxyethyl) phenyl] benzotriazole, 2- [2′hydroxy-5 ′-(methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2′-hydroxy-5 ′-(acryloyloxybutyl) )] Phenyl] -5-methylbenzotriazole, [2-hydroxy-3-t-butyl-5- (acryloyloxyethoxycarbonylethyl) phenol] benzotriazole, and the like.

[0013] The silicone macromer represented by the general formula (3) is useful for improving the antifouling property of a polyester resin building material surface.
It is used to enhance lubricity, and 1- (3-
It is obtained by an esterification reaction between (hydroxypropyl) polydimethylsiloxane and acrylic acid or methacrylic acid, or a reaction between 2-hydroxyethyl acrylate and 1- (3-glycidoxypropyl) polydimethylsiloxane. Specifically, 1- (3-methacryloxypropyl) polydimethylsiloxane, 3-methacryloxypropylpolydimethylsiloxane, polydimethylsiloxane methacrylamide and the like can be mentioned.

The ultraviolet absorbing monomers (1) and (2) in the monomer mixture and the silicone macromer (3)
Is preferably 90 to 99.95% by weight of the total of the ultraviolet absorbing monomers (1) and (2) and 0.05 to 10% by weight of the silicone macromer (3). If the UV-absorbing monomer exceeds 99.95% by weight, the proportion of the silicone macromer (3) becomes relatively low, so that film properties such as strength and lubricity are reduced,
The antifouling property may be insufficient. On the other hand, 90
If the amount is less than the percentage by weight, the ultraviolet absorbing ability is reduced, and as a result, the weather resistance of the polyester resin building material may be insufficient. The UV-absorbing monomers (1) and (2) may be used alone or in combination, and of the total weight of the UV-absorbing monomers (1) and (2), (1) is 100 to 0% by weight, and the ultraviolet absorbing monomer (2) is 0 to 100% by weight. In such an ultraviolet absorbing polymer, an ultraviolet absorbing monomer represented by the formula (1) and / or (2) and a formula (3)
Is covalently bonded to the silicone macromer represented by Therefore, even when this polymer is applied to the surface of a polyester film or the like as an ultraviolet absorber and used outdoors, the ultraviolet absorbing monomer hardly dissolves in rainwater. Therefore, the ultraviolet absorbing ability is maintained for a long time.

The monomer mixture may further contain a polymerizable vinyl compound copolymerizable with the above-mentioned ultraviolet absorbing monomers (1) and / or (2) and the silicone macromer (3). When a polymerizable vinyl compound is used, an ultraviolet absorbing polymer obtained by polymerizing a monomer mixture has excellent flexibility. Examples of such a polymerizable vinyl compound include acrylonitrile, alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, alkyl vinyl ester, and styrene. The alkyl group of acrylic acid alkyl ester, methacrylic acid alkyl ester, alkyl vinyl ether and alkyl vinyl ester is not particularly limited in the number of carbon atoms in the alkyl group. Is preferable and preferable.

Specific examples of these polymerizable vinyl compounds include, as alkyl (meth) acrylates, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl Methacrylate,
t-butyl methacrylate, 2-ethylhexyl methacrylate and the like. Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, and stearyl vinyl ether. Examples of the alkyl vinyl ester include vinyl acetate, ethyl vinyl, butyl vinyl, and 2-ethylhexyl vinyl. Among these polymerizable vinyl compounds, when methyl methacrylate or butyl acrylate is used, the obtained ultraviolet-absorbing polymer is particularly excellent in flexibility, and when applied to a film or sheet of polyester, the resulting film or sheet can be used. Does not impair flexibility. Therefore, for example, even when a polyester film coated with a UV-absorbing polymer is used for a greenhouse as an agricultural film, since this film easily follows the shape of the framework consisting of pipes,
Easy to assemble a greenhouse.

Further, the polymerizable vinyl compound copolymerizable with the ultraviolet absorbing monomers (1) and / or (2) and the silicone macromer (3) preferably contains a polymerizable vinyl compound having active hydrogen. . By using a polymerizable vinyl compound having active hydrogen,
Excellent in the strength of the coating made of the ultraviolet absorbing polymer and the adhesion to the surface of the building material. Examples of the polymerizable vinyl compound having active hydrogen include acrylic acid, methacrylic acid, maleic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylamide. Is more improved, acrylic acid and methacrylic acid are preferred.

When a polymerizable vinyl compound having active hydrogen is contained in the monomer mixture, a crosslinking agent is added to an ultraviolet absorbing polymer obtained by polymerizing the monomer mixture. It is preferably applied to the surface of a polyester resin building material. By adding the cross-linking agent, the strength, water resistance and weather resistance of the film composed of the ultraviolet absorber are more excellent. As the cross-linking agent, a methylol melamine resin, a glyoxal resin, a polyisocyanate-based cross-linking agent and the like can be used. In particular, trimethylol 3 mol adduct of toluene diisocyanate, trimethylol propane 3 mol adduct of hexamethylene diisocyanate, It is preferable to use a polyisocyanate-based cross-linking agent such as a 3 mol adduct of tolylene diisocyanate because of good adhesion to the polyester resin.

UV-absorbing monomers (1) and (2) in a monomer mixture and silicone macromer (3)
And the proportion of the polymerizable vinyl compound is such that the sum of the ultraviolet absorbing monomers (1) and (2) is 5 to 60% by weight, the silicone macromer (3) is 0.05 to 10% by weight, and the polymerizable vinyl compound is Is preferably 30 to 94.95% by weight. And, in the polymerizable vinyl compound, the polymerizable vinyl compound having active hydrogen in particular is 1 to 10% by weight.
Preferably, it is included. When the ultraviolet absorbing monomers (1) and (2) exceed 60% by weight in the monomer mixture, the coating properties such as strength and lubricity may be reduced,
If it is less than 5% by weight, the ultraviolet absorbing ability is reduced, and as a result,
The weather resistance of polyester resin building materials may be insufficient. In addition, 10% by weight of silicone macromer (3)
If the amount exceeds 0.05%, the uniformity and transparency of the coating may decrease. If the amount is less than 0.05% by weight, the lubricity of the coating may decrease and the antifouling property of the polyester resin building material may be insufficient. is there.

Such an ultraviolet absorbing polymer can be produced by a usual polymerization method such as a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. In the case of performing solution polymerization, a monomer mixture containing the ultraviolet absorbing monomers (1) and (2) and the silicone macromer (3) may be polymerized in a suitable solvent in the presence of a polymerization initiator. Examples of the polymerization solvent include known solvents such as esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, cyclohexane and methyl ethyl ketone, and ethers such as tetrahydrofuran. Can be used. These solvents can be used alone or in combination of two or more. Known polymerization initiators can be used, and examples thereof include peroxide compounds such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited, but is preferably about 0.05 to 2% by weight of the monomer mixture.

In particular, when the monomer mixture is of an aqueous emulsion type, a crosslinkable monomer may be further used as a copolymer component to form intra-particle crosslinking during emulsion polymerization. By forming the UV-absorbing polymer into an internal cross-linked structure in this way, when the UV-absorbing agent containing the polymer is applied to the surface of a building material such as a polyester film or sheet, it has excellent water resistance and weather resistance. A durable film can be formed. When polymerizing the aqueous emulsion type monomer mixture and the crosslinkable monomer, emulsion polymerization is carried out in an aqueous medium using an emulsifier and a water-soluble initiator.

A dye is added to the monomer mixture.
Colored UV-absorbing polymer particles may be produced to impart design properties. As the dye, DIANIX BLU
EBG-FSNEW (Mitsubishi Kasei Hoechst), DI
ANIX YELLOW G-FS (manufactured by Mitsubishi Kasei Hoechst), DIANIX RED KBN-SE (manufactured by Mitsubishi Kasei Hoechst) and the like. Further, the ultraviolet absorber used in the present invention may contain other additives as long as the object of the present invention is not impaired. For example, there are a hydrolysis inhibitor, an antioxidant, a fungicide, an antifoaming agent, and the like.
Examples of the hydrolysis inhibitor include carbodiimide-based stabacol 1, PCD (manufactured by Bayer), 4-t-butylcatechol, azodicarbonamide, and fatty acid amide. As an antioxidant, BH
T, Irganox1010, Irganox107
6, Cyanox 1790 and the like. Examples of the fungicide include pentachlorophenol, copper-8-hydroxyquinoline, and bis (tri-n-butyltin). As antifoaming agents, silicone,
Pluronic compounds and the like can be mentioned.

The polyester resin building material of the present invention can be applied to the surface of a polyester film, sheet, plate, etc.
Apply UV absorber containing UV absorbing polymer,
It can be manufactured by forming a coating. The application of the ultraviolet absorbent is performed by a usual method such as a brush coating method, a spray coating method, a dipping method, and a flow coating method. After the application, a heat treatment is appropriately performed to remove the solvent and water, thereby forming an ultraviolet absorbing film on the surface of the building material. The ultraviolet absorber is preferably formed so that the thickness of the film after drying is 1 to 10 μm. In addition, polyester resin building materials can be used for various applications such as decorative sheets, agricultural covering materials, transparent boards, transparent corrugated boards, etc. Therefore, it is particularly suitable for use in agricultural films used in greenhouses for cultivating agricultural crops. And among them,
It is most suitable for a house or a large house that is used continuously for a long period of 3 to 5 years or more. In the case of producing agricultural films, the polyester is calendered, T-die method, formed into a film having a thickness of about 0.01 to 0.5 mm by an inflation method, and then an ultraviolet absorber is applied to the surface, Form a coating.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. [Example 1] In a 1 L separable flask equipped with a Dim funnel, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer,
As shown in Table 1, 100.0 g of 2-hydroxy-4-methacryloyloxybenzophenone, silicone macromer (manufactured by Chisso Corporation, Silaprene FM-071)
1, molecular weight 1000) 20.0 g, 2-hydroxyethyl methacrylate 20 g, methyl methacrylate 60 g
And 2 g of n-dodecyl mercaptan and 200 g of methyl ethyl ketone, and the temperature was raised to 50 ° C. while blowing nitrogen from a nitrogen inlet tube. Thereafter, 1.0 g of azobisisobutyronitrile dissolved in a small amount of methyl ethyl ketone was added dropwise in 30 minutes, and after completion of the addition, the temperature was raised to 70 ° C., and the reaction was carried out for 8 hours to carry out an ultraviolet absorbing polymer having a molecular weight of about 20,000. Was manufactured. Then, a mixture of 100 g of the ultraviolet absorbing polymer and 5 g of a 75 wt% ethyl acetate solution of an adduct of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane was stirred and mixed into a polyethylene terephthalate film having a thickness of 0.15 mm. , And dried so as to have a thickness of 5 μm. Then, using a hot air dryer, 10
After drying and hardening at 0 ° C. for 2 minutes, a polyester film having a surface coated with an ultraviolet absorber was produced.

Example 2 An ultraviolet absorbing polymer was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and a polyester film was produced in the same manner. In addition,
The molecular weight of the ultraviolet absorbing polymer was about 50,000.

Example 3 An ultraviolet absorbing polymer was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and a polyester film was produced in the same manner. In addition,
The molecular weight of the ultraviolet absorbing polymer was about 40,000.

Example 4 An ultraviolet absorbing polymer was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and a polyester film was produced in the same manner. In addition,
The molecular weight of the ultraviolet absorbing polymer was about 60,000.

Example 5 200 g of ion-exchanged water was added to a 1 L separable flask equipped with a Dim funnel, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer, and heated to 70 ° C. while blowing nitrogen from the nitrogen inlet tube. The temperature rose. To each separately prepared container were added each monomer shown in Table 1, 10 g of Aqualon HS-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier, and 200 g of ion-exchanged water, followed by stirring to prepare a monomer emulsion. In another container, 60 g of deionized water, 2, 2
1 g of -'azobis [2- (2-imidazolin-2-yl) propane] hydrochloride was added to prepare a stirring dissolution initiator solution. The monomer emulsion and the initiator solution were simultaneously dropped into the separable flask over 2 hours. After completion of the dropwise addition, the mixture was further aged at 70 ° C. for 3 hours to prepare an emulsion type ultraviolet absorbing polymer. The solid content of this emulsion type ultraviolet absorbing polymer was 31 wt%, the particle diameter was 70 nm, and the molecular weight was 40,000. Then, a polyester film was manufactured in the same manner as in Example 1.

Example 6 An ultraviolet absorbing polymer was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and a polyester film was produced in the same manner.

Comparative Example 1 An ultraviolet absorbing polymer was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and a polyester film was produced in the same manner. In addition,
The molecular weight of the ultraviolet absorbing polymer was about 50,000.

Comparative Example 2 An ultraviolet absorbing polymer was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and a polyester film was produced in the same manner. In addition,
The molecular weight of the ultraviolet absorbing polymer was about 20,000.

[0032]

[Table 1] In the table, abbreviations indicate the following contents. UVA-1: 2-hydroxy-4-methacryloyloxybenzophenone UVA-2: 2-hydroxy-4-acryloyloxybenzophenone UVA-3: 2- [2′-hydroxy-5 ′-(methacryloyloxy) phenyl] benzotriazole UVA -4: 2- [2'-hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole UVA-5: 2- (3-t-butyl-5-methyl-2-
(Hydroxyphenyl) -5-chlorobenzotriazole Silicone Macromer-1: Thylaprene FM-07
11 (manufactured by Chisso Corporation, molecular weight: 1000) Silicone macromer-2: Silaplane FM-07
21 (manufactured by Chisso Corporation, molecular weight 5000) 2-HEMA: 2-hydroxyethyl methacrylate

Test Example 1 Examples 1 to 5 and Comparative Example 1
2 were evaluated for weather resistance, weather resistance, antifouling property, and transparency. The evaluation results are shown in Tables 2 and 3. 1. Evaluation of weather resistance The polyester film was treated with water / methanol = 5 at 60 ° C.
It was immersed in a 0/50 (weight ratio) mixed solvent for 24 hours. And, about the polyester film before and after immersion, the ultraviolet transmittance at a wavelength of 370 nm was measured with a spectrophotometer U-3200 manufactured by Hitachi, Ltd. 2. Evaluation of weather resistance I-Super SUV, a UV tester manufactured by Iwasaki Electric Co., Ltd.
Using -W13, a change in the polyester film before and after irradiation when the polyester film was irradiated with ultraviolet rays was visually evaluated. The irradiation cycle was performed up to 16. One cycle is a combination of 8 hours of light (ultraviolet irradiation) and 4 hours of dew (condensation state at 100% humidity). 3. Evaluation of antifouling property After leaving the polyester film in a constant temperature room at 70 ° C. for 30 minutes, sprinkle carbon black powder on the film,
It was left for another 30 minutes. The film was then allowed to cool to room temperature. Then, water was sprayed on the film tilted obliquely using a spray (a distance between the spray and the film of 20 c).
m, number of sprays 50). Thereafter, the film was dried at room temperature, and the state of contamination at that time was visually observed and evaluated. 4. Evaluation of Transparency The haze value of the polyester film was measured using a haze meter.

[0034]

[Table 2] In the table, abbreviations indicate the following contents. ：: no stain △: slight stain remaining ×: stain remaining

[0035]

[Table 3] In the table, abbreviations indicate the following contents. ：: No change △: Yellowing ×: Cracking on the surface

The following became clear from the table. -Weather resistance The polyester films obtained in Examples 1 to 6 had an ultraviolet transmittance before and after immersion in the mixed solvent because the ultraviolet absorber applied and formed on the film surface hardly dissolved in the mixed solvent. Hardly changed, and a low ultraviolet transmittance was maintained. That is, it was suggested that, even when the polyester films obtained in Examples 1 to 6 were used outdoors, the ultraviolet absorber hardly eluted in water such as rainwater, and excellent weather resistance was maintained. On the other hand, in the polyester film of Comparative Example 1, the UV absorber applied to the surface was eluted into the mixed solvent, and the UV transmittance increased. -Weather resistance The polyester films obtained in Examples 1 to 6 showed no change even when irradiated with ultraviolet rays corresponding to an actual exposure level of 6 years or 8 years, and were excellent in weather resistance. On the other hand, the polyester films obtained in Comparative Examples 1 and 2,
The actual exposure level was slightly yellowed by ultraviolet irradiation corresponding to 6 years, and the actual exposure level was significantly yellowed by ultraviolet irradiation corresponding to 8 years. -Antifouling property When the polyester films obtained in Examples 1 to 6 were sprayed with water, carbon black flowed down with the water. On the other hand, in the polyester films obtained in Comparative Examples 1 and 2, carbon black powder remained on the entire film surface even after spraying water. -Transparency The polyester films obtained in Examples 1 to 6 were excellent in transparency.

[0037]

As described above, the polyester resin building material of the present invention comprises an ultraviolet absorbing monomer having a specific structure,
A coating made of an ultraviolet absorber containing an ultraviolet absorbing polymer obtained by polymerizing a monomer mixture containing this ultraviolet absorbing monomer and a specific copolymerizable silicone macromer is formed. And in this ultraviolet absorber,
An ultraviolet absorbing monomer is covalently bonded to the polymer. Therefore, even when the polyester resin building material of the present invention is used outdoors for a long time as an agricultural film used for a greenhouse, the ultraviolet absorbent does not elute, the ultraviolet absorbing ability is maintained, and the film surface is maintained. The antifouling property is hardly deteriorated. Also, it has excellent transparency. Furthermore, the monomer mixture further contains a polymerizable vinyl compound copolymerizable with an ultraviolet absorbing monomer and a silicone macromer, whereby an ultraviolet absorbing polymer having excellent flexibility can be obtained, which is used for a polyester resin building material. It becomes more suitable. Furthermore, since the polymerizable vinyl compound contains a polymerizable vinyl compound having active hydrogen, the strength of the coating and the adhesion to building materials are excellent. The polyester resin building material of the present invention is particularly suitable for use as an agricultural film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 4J035 C08G 77/442 C08G 77/442 C09K 3/00 104 C09K 3/00 104A 104C E04F 13/00 E04F 13/00 B // C08L 67:02 C08L 67:02 (72) The inventor Saiji Sugimori 1516-1 Odamachi, Ono-shi, Hyogo Pref. Ryuichi 1516-1 Oda-cho, Ono-shi, Hyogo On the other hand, F-term (reference) 2B024 DA05 DB01 2B029 EB02 EC03 EC09 EC14 EC19 RA03 4F006 AA35 AB12 BA03 CA06 4F100 AK41B AK42 AK52A BA02 BA07 CA02A CA07A J07J06 J07N YY00A 4J027 AF04 AF06 BA07 BA13 CD08 4J035 GA02 GB01 GB08 GB09 LB01

Claims (6)

[Claims] 1. A building material made of a polyester resin on which a film made of an ultraviolet absorber is formed, wherein the ultraviolet absorber comprises an ultraviolet absorbing monomer represented by the following general formula (1) and / or (2): A building material made of a polyester resin, characterized by containing a UV-absorbing polymer obtained by polymerizing a monomer mixture containing an absorbing monomer and a silicone macromer represented by the following general formula (3) that can be copolymerized. Embedded image (In Formula 1, R ₁ represents any _one of hydrogen, an alkyl group having 1 to 6 carbon atoms, or an oxyalkyl group, and R ₂ represents an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group, or an absent. If R ₂ is absent, then X
Is directly bonded to the benzene ring. X represents any of an ester bond, an amide bond, an ether bond and a urethane bond. R ₃ represents hydrogen or a lower alkyl group. ) (In the formula 2, R ₄ represents any one of hydrogen, halogen, and methyl group, R ₅ represents hydrogen or a hydrocarbon group having 1 to ₆ carbon atoms, R ₆ represents an alkylene group having 1 to 10 carbon atoms, R represents either an oxyalkylene group or absent.
_{When 6} indicates absent, Y is directly bonded to the benzene ring. Y represents an ester bond, an amide bond, an ether bond or a urethane bond. R ₇ has 1 to 8 carbon atoms
Represents an alkylene group, an aminoalkylene group, an alkyl group having a hydroxyl group in a side chain, or absent.
When R ₇ is absent, Y and C are bonded directly. R ₈ represents hydrogen or a lower alkyl group. ) (In the formula 3, R ₉ represents hydrogen or a methyl group, R ₁₀ represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group, or absent. When R ₁₀ represents absent,
And Z are directly bonded. Z represents an ester bond or an amide bond. R ₁₁ represents an alkylene group having 1 to 6 carbon atoms, an aminoalkylene group, an alkyl group having a hydroxyl group in a side chain, or absent. When R ₁₁ is absent, Z and Si are directly bonded. N is an integer of 10 to 200. ) 2. The monomer mixture according to the general formula (1) and / or
The polyester resin according to claim 1, further comprising a polymerizable vinyl compound copolymerizable with the ultraviolet absorbing monomer represented by (2) and the silicone macromer represented by the general formula (3). Building materials. 3. The polymerizable vinyl compound contains a polymerizable vinyl compound having active hydrogen.
A building material made of a polyester resin according to the above. 4. The polyester resin building material according to claim 3, wherein the ultraviolet absorber further comprises a polyisocyanate-based crosslinking agent. 5. The ultraviolet absorbing polymer having a molecular weight of 10,000 to 3
The polyester resin building material according to any one of claims 1 to 4, wherein the building material is 0,000. 6. The polyester resin building material according to claim 1, wherein the building material is an agricultural film.