KR20000027779A - Resin composition for decorative polyester film and preparation method thereof - Google Patents

Abstract

PURPOSE: A resin composition of preparing a polyester film for decoration and preparation method thereof are provided which have improved physical properties such as antibacterial and hiding properties. CONSTITUTION: A resin composition for manufacturing at least uniaxially oriented polyester film for decoration comprises (a)a polyester resin containing at least 60 parts or more by weight of ethyleneterephthalate units and having a limit viscosity of 0.4 to 0.9 dl/g, (b)1 to 20 parts by weight of a coloring agent based on the 100 parts by weight of a polyester resin and (c)0.1 to 10 parts by weight of a porous solid matter coated with 100 to 1,000 ppm/g of a metal ion selected from Ag, Cu and Zn based on the weight of the solid mater having a specific surface area of 10 to 30 m¬2/g and a particle diameter of 0.1 to 5 micrometer. Also described is a method for preparing the film which comprises (A)preparing an amorphous sheet by melt extruding the composition, (B)coating with an aqueous polymeric dispersion to a thickness of 0.001 to 0.5 micrometer, mixed with 0.5 to 20 parts by weight of a sulfonated polyester copolymer resin and a thermosetting urethane prepolymer resin containing a hydrophilic radical based on the weight of the aqueous polymeric dispersion and (C)heat treating the coated film at a temperature of 190 to 250°C. The film is useful as a plywood lamination, an interior ornament containing wall paper and a use for packaging foodstuffs.

Description

Resin composition for manufacturing decorative polyester film and method for producing same

The present invention relates to at least uniaxially oriented polyester films with improved physical properties, in particular hiding power, antibacterial properties, ink adhesion and running properties. These are particularly useful in applications such as plywood lamination, interior decoration including wallpaper, and food packaging applications.

The plastic film is made of various materials such as polyethylene terephthalate and polypropylene and polyvinyl chloride. In particular, polyvinyl chloride has been predominantly used for interior decoration such as plywood lamination.However, due to the increased awareness of environmental protection, the market is gradually decreasing despite the high utility due to strong environmental regulations. There is a trend.

Due to these problems, the use of polyolefins or polyesters is increasing, among which polyester is superior in terms of mechanical strength and stability. In particular, polyethylene terephthalate has both chemical and physical stability, high mechanical strength, and durability. It has excellent advantages such as heat resistance, chemical resistance, electrical insulation, and unlike the existing polyvinyl chloride film, it is completely harmless to human body, so it can be used for food packaging.

On the other hand, in recent years, the demand for hygiene has increased, as well as food packaging containers, various items such as storage boxes, kitchens, bathtubs, etc. are also increasing the demand for materials that can be attached to the antibacterial properties to grow and grow. In order to solve this need, attempts to maintain freshness of vegetables using inorganic fine particles have been disclosed in Japanese Laid-Open Patent Publication Nos. 63-86757, Hei 2-147059, Hei 2-101003, Hei 2-147059, Hei 4-21614, and the like. In addition, a technique that provides antibacterial and deodorant properties by using an adsorbent inorganic material is disclosed in H1-207339. However, even though such techniques have been disclosed, there is a limit to increase the antibacterial effect simply based on the inorganic material itself.

Accordingly, an object of the present invention is to provide a polyester resin composition for producing a polyester film having antimicrobial and hiding properties.

Another object of the present invention is to provide a method for producing a polyester film having improved physical properties such as antimicrobial and hiding properties by using the polyester resin composition.

According to one aspect of the invention,

(a) a polyester resin containing at least 60 parts by weight or more of ethylene terephthalate units and having an intrinsic viscosity of 0.4 to 0.9 dl / g;

(b) 1 to 20 parts by weight of a colorant capable of imparting hiding power to the resin based on 100 parts by weight of the polyester resin; And

(c) Specific surface area of 10-30 m ² / g based on 100 parts by weight of polyester resin, 0.1-5 μm of particle diameter, and metal ions selected from Ag, Cu and Zn were coated with 100-1000 ppm / g based on the solid content weight. A composition consisting of 0.1 to 10 parts by weight of porous solid content is provided.

According to the second aspect of the present invention,

(A) melt-extruding the polyester resin composition of the first aspect to produce an amorphous sheet;

(B) the weight of the aqueous dispersion of a thermosetting urethane prepolymer resin having a hydrophobic group and a polyester copolymer resin containing a sulfonate component on at least one side of the film prepared by longitudinally aligning the sheet or sheet prepared in step (A) Coating a water dispersion mixed in an amount of 0.5 to 20 parts by weight with a thickness of 0.001 to 0.5 µ; And

(C) heat-treating the coated film at a temperature of 190 ~ 250 ℃; a method is provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention to solve the above problems (a) polyester resin; (b) a colorant capable of imparting hiding power to the resin; And (c) porous antimicrobial solids coated with metal ions; A composition consisting of is provided.

The said polyester resin (a) condensates the acid component which has aromatic dicarboxylic acid as a main component, and the diol component which has alkylene glycol as a main component.

Specific examples of the aromatic dicarboxylic acid include dimethyl terephthalate, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, 5-sulfoisophthalic acid, 5-sulfopropoxyisophthalic acid, diphenyldi Carboxylic acid, diphenoxyalkanedicarboxylic acid, adipic acid, sebacic acid, and the like, of which dimethyl terephthalate or terephthalic acid is particularly preferable. The polyester resin of the present invention is a single polyester of 60 parts by weight or more made of polyethylene terephthalate, and at least one or more of the dicarboxylic acids and diol components listed above may be copolymerized or added within 40 parts by weight of the balance.

Examples of the diol component include alkylene glycols such as ethylene glycol, 1,3-propanediol and 1,4-butanediol, 2,2-dimethyl-1,3-propanediol and 1,4-cyclohexanedimethanol Ethylene glycol is particularly preferred.

The polyester resin used in the present invention has an intrinsic viscosity of 0.4 to 0.9 dl / g, preferably 0.5 to 0.5, in a concentration of 0.05%, 0.1% and 0.15% in 25 ml of orthochlorophenol at 35 ° C. 0.8 dl / g. If the intrinsic viscosity is 0.4 dl / g or less, when the polyester film of the present invention is produced, breakage during stretching is frequent and productivity is extremely low, and mechanical strength of the final product is not preferable. In addition, when the intrinsic viscosity is more than 0.9 dl / g, the melt viscosity during the extrusion process is too high, resulting in difficulties such as extrusion instability.

In the present invention, a method of imparting hiding power and color to the polyester resin is as follows. In order to impart hiding power, at least one pigment should be basically used. Particularly, it is convenient to use a titanium dioxide to color the film.

In addition, a pigment or dye having heat resistance that can withstand a melt extrusion process of about 285 to 295 ° C. should be used, and two or more pigments and / or dyes may be mixed and used to impart a desired color.

Examples of suitable pigments for use in the present invention include titanium dioxide, barium sulfate, carbon black, chromate pigments, azo pigments, quinacridones and dyeing lakes, and examples of dyes include monoazo, disazo, anthraquinone, Both pigments and dyes on the color index may be used as the batt dye, the modant dye, or the like.

Pigment and dye concentration in the final film can be freely adjusted according to the desired shade of color, but is preferably used within 1 to 20 parts by weight per 100 parts by weight of the polyester resin. If the added amount is 1 part by weight or less, it is difficult to obtain the target concealability, and if it is 20 parts by weight or more, the physical properties of the film, such as mechanical strength, deteriorate, and breakage occurs frequently during the production process, which is not preferable.

In the present invention, a method of adding a pigment and a dye to the polyester resin may be both a direct addition method and a master batch method. Direct dosing method is to add each additive to the desired concentration of ethylene glycol slurry and directly do it during transesterification or condensation polymerization. It is a useful method for mass production. In the master batch method, all or part of the additives is added at high concentration. After preparing a polyester resin, and then extruded by mixing with the polyester resin is not added to the additive, it is easy to adjust to the desired concentration and is suitable for producing small quantities of various kinds.

As a technique for providing antimicrobial activity in the present invention, a method of increasing antimicrobial activity by active oxygen is used. By oxygen in the air reacts with the metal ion constituting the adsorption layer on the solid surface of the antimicrobial activity of high superoxide (superoxide, O ₂ ^-) there is generated to which inhibits activation of the enzyme, and inhibition of protein synthesis antibacterial effect Maximize.

In order to maximize the antimicrobial action, an antimicrobial agent that can actively react with oxygen in the air should be applied. Such antimicrobial agents can be classified into organic and inorganic antimicrobial agents. In the case of organic antimicrobial agents, there is a risk of harm to the human body due to its constituents, and thermal stability is deteriorated. In this case, there is a disadvantage in that the physical properties of the plastic product is slightly impaired, but not only can be improved by additional conditions or application conditions, but also harmless, permanent and incidental far-infrared effect of the solid can be obtained.

Accordingly, in the present invention, 0.1 to 10 parts by weight of zirconium phosphorus compound, calcium phosphorus compound, zeolite, silica compound, ceramics and the like are added as the inorganic antibacterial solid content per 100 parts by weight of the polyester resin. More preferably, most of the components are made of a stable material, which is excellent in heat resistance and light resistance, has a far-infrared effect of more than 90% at 40 ° C, and it is preferable to use a zeolite or a silica compound which can obtain sterilization and antibacterial effects. . In addition, solidifying at high temperatures prior to use can maximize this effect.

The larger the specific surface area of the solid, the greater the ability to produce superoxide. However, when the specific surface area is too large, it is not preferred the particles are atomized reduced physical properties such as dispersibility, when a specific surface area of less than 10m ² / g, can not be expected to a sufficient antimicrobial activity, a specific surface area of ² 10~30m / g is preferred. For the same reason, the range of the particle size is also preferably 0.1 to 0.5 mu.

In addition, when the inorganic antimicrobial solids are coated with Ag, Cu, and Zn ions in Group Ib and Group IIb metal ions, the antimicrobial activity is significantly increased. In this way, by coating metal ions with a monoatomic layer or polyatomic layer on the entire interface or part of the surface of the solid, the oxygen and ion exchange in the air can be further activated to maximize superoxide generation ability and maximize antibacterial effect. have. Adsorption amount of metal ions is suitable from 100 to 1000ppm / g based on the inorganic antimicrobial solid content, if less than 100ppm / g can not achieve the desired effect, if it exceeds 1000ppm / g is not only difficult to apply, but also increased coating amount The effect is minimal.

The polyester resin composition as described above is melt-extruded and solidified on a rotating casting drum to obtain an amorphous cast sheet. Prior to orienting the sheet thus obtained or at least one axial axis, an ink dispersion and runability are also improved by applying an aqueous dispersion of polyester copolymer resin, water dispersible urethane resin, and inorganic particles to at least one surface of the sheet or film. Can be.

The polyester copolymer resin is a water-soluble or water-dispersible resin obtained by transesterification and polycondensation of dicarboxylic acid and diol and composed of 85 mol% or more of aromatic dicarboxylic acid and 15 mol% or less of sulfonic acid-containing dicarboxylic acid substituted with alkali metal salt. The average molecular weight is less than about 50,000, preferably 25,000 or less, and the glass transition temperature is 80 ° C or less. If the molecular weight is too high, the water dispersibility is worse, if the glass transition temperature is too high, the effect of improving the adhesive force is lowered, which is undesirable. The aromatic dicarboxylic acid and diol used in the polyester copolymer resin production are as described above.

Sulfonate-containing dicarboxylic acids are used herein to provide water dispersibility and adhesion to polyesters, and suitable examples include sodium sulfophthalic acid, 5-sodium isophthalic acid, 5-sulfoisopropoxy isophthalic acid, and the like.

It is preferable that a water-dispersible urethane resin contains the urethane bond obtained by condensation polymerization of the polyol which is an active hydrogen compound, and polyisocyanate in a principal chain, and has a hydrophilic group at the terminal. Examples of the polyol component include, but are not limited to, polyester polyols containing terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or the like, or polyether polyols or other known polyols polymerized with alkylene oxides and active hydrogen compounds.

Examples of the polyisocyanate component include 5-isocyanate-1-isocyanatemethyl-1,3,3-trimethyl cyclohexane, 2,4-hexamethylene diisocyanate and 2,6-hexamethylene diisocyanate.

The resin components are used 0.5 to 20 parts by weight based on the weight of the aqueous dispersion, more preferably 1 to 18 parts by weight. On the other hand, if the concentration is 0.5 parts by weight or less, no effect can be obtained. If it is 20 parts by weight or more, it is not economical and the dispersibility is poor. When the aqueous dispersion is used alone, ink adhesion may be increased but runability may deteriorate. Therefore, by selecting at least one inorganic particle among silica, calcium carbonate, and alumina, 0.1 to 1.0 parts by weight based on the weight of the aqueous dispersion is added. By coating, the running property of a film is also improved. When the density | concentration of the said inorganic particle is 0.1 weight part or less, the running property improvement effect which is the objective of this invention cannot be expected, and when it is 1.0 weight part or more, adhesiveness will fall and it is unpreferable. It is preferable that the particle diameter of an inorganic particle is 0.1-1.0 micrometer at this time.

The method of applying the aqueous dispersion to the film prepared as described above may be any known method, for example, a roll method or a Meyer bar method, and the thickness of the final dried coating liquid is preferably 0.001 to 0.5 µm. Is in the range of 0.005 to 0.2 µ. If it is 0.001μ or less, there is no effect of coating, and it is difficult to apply the coating to 0.5μ or more, and the effect on increasing the coating amount is insignificant.

In some cases, the prepared polyester film may be heat-treated to impart dimensional stability and excellent tensile properties. At this time, the heat treatment temperature is preferably 190 to 250 ° C in view of the thermal properties of the resin. If it is out of this range, it will not be melted or heat treated.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are illustrative and are not intended to limit the invention.

Physical properties of the film prepared in the following Examples were evaluated using the following method.

<Method for evaluating physical properties of film>

(1) color

Visual inspection in natural light was performed using Universal Color Language 1st stage.

(2) hiding power

The spectrophotometer 3500D from Monoita, Japan, was used to evaluate the hiding power by measuring the color difference between the black and white reflectors. The smaller the value of the color difference, the greater the hiding power.

(3) antimicrobial activity

Test bacteria were contacted with specimens using Escherichia coil (ATCC 25922) as a strain, followed by standing culture at 25 ° C. for 24 hours, and antimicrobial activity was measured. The fewer the bacteria, the better the antimicrobial activity.

(4) ink adhesion

After applying the ink on the surface of the film was dried for 1 minute at 100 ℃ and the cellophane tape of Korea Daeilsa firmly attached to the ink layer was repeated three times the process of instant peeling. Adhesion was determined to the extent that the applied ink remained on the substrate,

○ (excellent): when the ink layer remains on the substrate to some extent after three peel

△ (normal): when no ink layer remains on the substrate after peeling twice or three times,

× (defect): The case where the ink layer did not remain in a base material after 1 peeling was shown.

(5) coefficient of friction

Friction coefficients were measured under the conditions of 1.0 kg load and 150 mm / min speed using a surface tester (Model 2227001) manufactured by Seiseku-sho, Japan.

<Example 1>

4 parts by weight of titanium dioxide, 1 part by weight of red iron oxide, 0.7 parts by weight of chromium yellow, and 0.01 parts by weight of carbon black were added to a single polyethylene terephthalate resin having an intrinsic viscosity of 0.651 dl / g, with a specific surface area of 15 m ² / g. 6 parts by weight of the silica compound was added and kneaded to prepare a brownish polyethylene terephthalate resin.

In this case, porous silica was used by first coating 170 ppm / g of Cu metal ions by dissolving 0.05% Cu ₂ O. The resin thus obtained was extruded at 285 ° C. to produce an amorphous sheet and stretched three times in the longitudinal direction.

Thus, the uniaxially stretched film was uniformly coated with a thickness of 0.05 mu in the Mayer method before the transverse stretching was performed. At this time, the coating liquid is 8 parts by weight of a polyester copolymer resin containing a main component of the repeating unit is ethylene terephthalate, 30 mol% of ethylene isophthalate and 8.5 mol% of a 5-sulfoisophthalic acid component and a polyurethane prepolymer as auxiliary components. An aqueous dispersion comprising 0.5 parts by weight and 0.8 parts by weight of silica having an average particle diameter of 0.5 mu.

After the application was completed, it was continuously stretched three times in the transverse direction at about 130 ° C. and heat-set at 210 ° C. with a thickness of 50 μ. The film thus produced had a brown color, and hiding power, running property, antibacterial property and ink adhesion were all excellent as shown in Table 1.

<Examples 2-5>

The same procedure as in Example 1 was repeated except that the conditions were changed as described in Table 1 below. The physical properties of the films thus produced are also shown in the table below.

Comparative Example 1

The same procedure as in Example 1 was repeated except that only dye was added without adding a pigment. The dye to be added is 4 parts by weight of C.I. Disperse Yellow 13 and 1 part by weight of C.I.Solvent Blue 11. The physical properties of the film thus prepared were markedly low as described in the following table.

<Comparative Examples 2-5>

It was prepared in the same manner as in Example 1 except that the conditions were changed as described in Table 1 below. Physical properties of the produced film were generally poor as shown in the following table.

* (Used amount of each of polyester copolymer resin and polyurethane prepolymer resin).

According to the present invention, it is possible to produce a polyester film in which physical properties such as concealability, antibacterial property, ink adhesion property and running property are well harmonized.

Claims (13)

(a) a polyester resin containing at least 60 parts by weight or more of ethylene terephthalate units and having an intrinsic viscosity of 0.4 to 0.9 dl / g; (b) 1 to 20 parts by weight of at least one pigment and / or optionally dyes capable of imparting hiding power to the resin based on 100 parts by weight of the polyester resin; And (c) Specific surface area of 10-30 m ² / g based on 100 parts by weight of polyester resin, 0.1-5 μm of particle diameter, and metal ions selected from Ag, Cu and Zn were coated with 100-1000 ppm / g based on the solid content weight. 0.1 to 10 parts by weight of porous solids, consisting of a resin composition for producing a polyester film with improved antimicrobial and hiding properties The composition of claim 1, wherein the polyester resin (a) is prepared by adding at least one or more of aromatic dicarboxylic acid and diol component within 40 parts by weight based on the total weight of the resin. The method of claim 2, wherein the aromatic dicarboxylic acid is dimethyl terephthalate, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, 5-sulfoisophthalic acid, 5-sulfopropoxyisophthalic acid, Composition selected from the group consisting of diphenyldicarboxylic acid, diphenoxyalkanedicarboxylic acid, adipic acid and sebacic acid The composition of claim 2, wherein the diol is selected from the group consisting of alkylene glycols, 2,2-dimethyl-1,3-propanediol and 1,4-cyclohexanedimethanol The method of claim 1, wherein the pigment (b) is selected from titanium dioxide, barium sulfate, carbon black, chromate pigment, azo pigment, quinacridone and dyeing lake, the dye is monoazo, disazo, anthra Composition selected from quinones, vat dyes and modant dyes The composition according to claim 1, wherein the porous antimicrobial solid (c) is selected from the group consisting of zirconium phosphorus compounds, calcium phosphorus compounds, zeolites, silica compounds and ceramics. (A) melt extruding and solidifying the polyester resin composition of claim 1 to prepare an amorphous sheet; (B) at least one surface of the film prepared by longitudinally aligning the amorphous sheet or sheet prepared in step (A), a thermosetting urethane prepolymer resin having a hydrophobic group and a polyester copolymer resin containing a sulfonate component Applying a water dispersion mixed in an amount of 0.5 to 20 parts by weight based on the weight in a thickness of 0.001 to 0.5 µ; And (C) when the aqueous dispersion is applied to the sheet in the step (B) to produce a film by transversely oriented the sheet, and then heat-treating the applied film at a temperature of 190 ~ 250 ℃; In addition, polyester film manufacturing method with improved dimensional stability, tensile property and ink adhesion The method of claim 7, wherein the polyester copolymer resin containing the sulfonate component is 85 mol% or more is aromatic dicarboxylic acid and 15 mol% or less is obtained by transesterification and polycondensation of dicarboxylic acid and diol which is an alkali metal salt substituted sulfonic acid, The number average molecular weight is less than about 50,000, characterized in that the glass transition temperature is 80 ° C or less water-soluble or water-dispersible resin. The method of claim 8, wherein the aromatic dicarboxylic acid is dimethyl terephthalate, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, 5-sulfoisophthalic acid, 5-sulfopropoxyisophthalic acid, Composition selected from the group consisting of diphenyldicarboxylic acid, diphenoxyalkanedicarboxylic acid, adipic acid and sebacic acid According to claim 8, wherein the diol is alkylene glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol and 1,4-cyclohexane Compositions selected from the group consisting of dimethanol The method of claim 8, wherein the alkali metal salt substituted sulfonic acid is selected from the group consisting of sodium sulfophthalic acid, 5-sodium isophthalic acid and 5-sulfoisopropoxy isophthalic acid. 8. The method according to claim 7, wherein the thermosetting urethane prepolymer resin includes a urethane bond obtained by condensation polymerization of a polyol and a polyisocyanate as an active hydrogen compound in the main chain and has a hydrophilic group at its terminal. According to claim 7, at least one selected from the group consisting of silica, calcium carbonate and alumina having a particle diameter of 0.1 to 1.0μ in the aqueous dispersion of step (B) 0.1 to 1.0 weight based on the weight of the aqueous dispersion Method for improving runability by using by addition