KR20080051629A - Copolyester resin composition and articles using the same - Google Patents

Abstract

A copolyester resin composition is provided to produce translucent copolyester sheets having reduced transparency without using a separate coating process. A copolyester resin composition includes (i) 100 parts by weight of a copolyester resin having an intrinsic viscosity of 0.60-1.0 dl/g, and (ii) 30-60 parts by weight of an inorganic additive having a particle size of 2-50 micron. The copolyester resin is obtained by subjecting (i) a dicarboxylic acid component comprising terephthalic acid, and (ii) a diol component comprising 0.1-99.0 mol% of 1,4-cyclohexanedimethanol and 0.1-99.9 mol% of ethylene glycol to esterification and polycondensation.

Description

Copolyester resin composition and articles using the same {Copolyester resin composition and articles using the same}

The present invention relates to a copolyester resin composition and a molded article using the same. More specifically, the present invention relates to a copolymerized polyester resin composition and a molded article using the same, by adding an inorganic additive for improving surface roughness to a copolymerized polyester resin to prepare an advanced interior translucent sheet without a separate coating process. .

In general, in the case of a sheet made of copolyester resin (PETG) mainly composed of 1,4-cyclohexanedimethanol as a raw material, the sheet is transparent and its gloss is expressed on the surface of the sheet.

On the other hand, the matte effect or translucent effect is sometimes used as a high-grade interior sheet or frame cover. Until now, the surface of the sheet is processed like a glazed glass by processing the surface of the cooling roll to give a matte or translucent effect on the plastic sheet. It has adopted a method of making the sheet opaque by making light diffusely reflected. At this time, roughening the surface and implementing a kind of matt effect is known as an important technique for producing high-quality sheets by implementing diffuse reflection of light on the surface.

However, in the case of the copolyester resin, even if the processed cooling roll is used, the surface is smooth again because cooling is slow, and this method cannot be used. In this case, a method of reducing transparency by mixing a certain amount of inorganic materials such as silica or talc is used. However, when using this method, the simple addition of inorganic materials such as silica or talc does not show the effect of improving the surface roughness, and can only be realized by the effect of blurring. In addition, when the particle size is used below the predetermined size to improve the dispersion, the surface roughness effect is not properly realized, so that the surface glossiness is poor. Therefore, the use of inorganic particles having a certain ratio and a predetermined size or more does not make the surface smooth by the particles. For this reason, when a thick sheet is manufactured, the sheet and the cooling roll do not adhere well, and thus the sheet is separated from the cooling roll. .

Accordingly, the present invention is to provide a molded article such as a semi-transparent sheet based on the copolyester resin composition that can solve all the problems of the prior art as described above.

In order to solve the above problems, the present inventors have increased by extruding or injection molding a copolymerized polyester resin composition obtained by adding an inorganic additive having a property of increasing the physical properties of a polymer to a copolymerized polyester resin at a predetermined size and a predetermined ratio. It was possible to obtain molded articles having improved surface roughness and improved hardness. The molded product is not significantly damaged even if the temperature of the cooling roll is increased by a predetermined ratio or more, and thus the non-adhesion phenomenon of the sheet and the cooling roll that occurs when a thick translucent sheet is manufactured using ordinary silica or talc particles is produced. Does not appear Through this, it is possible to obtain a haze increase effect due to the difference in refractive index between the inorganic particles and the copolymer polyester resin penetrated into the copolymer polyester resin, and the inorganic particles are distributed on the sheet surface in large amounts so that the copolymer poly The intrinsic glossiness of the ester resin is primarily removed and opaque to complete the present invention by knowing that a matte translucent sheet can be produced without a separate coating process.

Co-polyester resin composition according to a preferred embodiment of the present invention,

(i) 100 parts by weight of copolymerized polyester resin having an intrinsic viscosity of 0.60 to 1.0 dl / g; And

(ii) 30 to 60 parts by weight of an inorganic additive having a particle size of 2 to 50 µm;

Characterized in that it comprises a.

The (i) copolyester resin is preferably a dicarboxylic acid component containing terephthalic acid, and a diol containing 0.1 to 99.9 mol% of 1,4-cyclohexanedimethanol and 0.1 to 99.9 mol% of ethylene glycol. The components were subjected to esterification reaction and polycondensation reaction. More preferably, the diol component comprises 10 to 90 mole% 1,4-cyclohexanedimethanol and 10 to 90 mole% ethylene glycol.

The inorganic additive is preferably selected from the group consisting of silica oxide, magnesium oxide, calcium carbonate, iron oxide, talc and combinations thereof.

The copolyester resin composition may further include an additive selected from the group consisting of phosphorus-based additives, waxes, antioxidants, inorganic matting agents, and combinations thereof.

The molded article according to one preferred embodiment of the present invention is characterized in that the resin composition is formed by (co) injection or (co) extrusion molding.

The molded article preferably has a gloss of 30 or less, haze 50-95 and transmittance 50-95%.

The molded article may be a sheet having a single layer or a multilayer structure, and when the molded article is a sheet having a multilayer structure, an outer surface layer of the sheet is formed from the resin composition according to the present invention.

Hereinafter, the present invention will be described in more detail.

As described above, in the present invention, a copolymerized polyester resin composition comprising a copolymerized polyester resin having an intrinsic viscosity of 0.60 to 1.0 dl / g and an inorganic additive that increases the rigidity of the internal polymer chain, and a translucent sheet to which the same is applied. The same molded product is provided.

The copolyester resin used in the present invention has an intrinsic viscosity of 0.60 to 1.0 dl / g, preferably 0.70 to 0.80 dl / g. When the intrinsic viscosity of the copolyester resin is less than 0.60 dl / g, product physical properties are difficult to express, and when it exceeds 1.0 dl / g, molding is difficult.

The copolyester resin consists of a dicarboxylic acid component and a diol component. The dicarboxylic acid component includes terephthalic acid, and in addition, isophthalic acid and other acid components may be used as necessary. The diol component includes 1,4-cyclohexanedimethanol and ethylene glycol, and other diol components may be used as necessary. As the copolyester resin, a transparent copolyester resin including 0.01 to 99.9 mol% of a diol component may be used as compared to 100 mol% of terephthalic acid, and preferably 10 to 90 mol% of the diol component, more preferably 20 It contains-40 mol%.

The diol component preferably comprises 0.1 to 99.9 mol% of 1,4-cyclohexanedimethanol and 0.1 to 99.9 mol% of ethylene glycol, and more preferably 10 to 90 mol% of 1,4-mol. Cyclohexanedimethanol and 10-90 mole% ethylene glycol.

The inorganic additive used in the present invention has a particle size of 2 to 50 µm, preferably 5 to 30 µm, and the amount of the inorganic additive used is 30 to 60 parts by weight, preferably 30 to 30 parts by weight of the copolymerized polyester resin. 45 parts by weight. When the particle size of the inorganic additive is less than 2㎛ the surface roughness effect due to the inorganic particles derived to the surface due to the small particle size does not appear properly, when the particle size exceeds 50㎛ the inorganic material is too large There is a disadvantage that the dispersion of particles is not properly. In addition, in the case where the inorganic additive content exceeds 60 parts by weight, especially in the case where the master batch is used, when the inorganic additive content in the master batch exceeds 60 parts by weight, the production of the inorganic additive becomes very difficult, resulting in poor workability, and 30 parts by weight. If the amount is less than the amount of the inorganic material has a disadvantage in that the surface matting effect is not properly implemented and the glossiness is increased.

As the inorganic additive, it is preferable to select and use any one or a combination of two or more of silica oxide, magnesium oxide, calcium carbonate, iron oxide, and talc, but it is particularly limited so long as it can obtain a predetermined effect desired in the present invention. All of them can be used.

The composition of the present invention may further include an epoxy-based additive, the amount of the additive may vary from 0.001 to 20 parts by weight with respect to 100 parts by weight of the copolymerized polyester resin, preferably 0.005 to 10 parts by weight, more preferably 0.005 It is-5 weight part. When the added amount is less than 0.001 parts by weight, it is difficult to implement the translucent effect, and when it exceeds 20 parts by weight, the transmissivity is too low to express the effect of the luxurious translucent sheet.

In addition, additives such as phosphorous additives, waxes, antioxidants, inorganic matting agents, and the like may be optionally added in order to increase injection and extrusion flowability and high temperature temperature stability and add translucency and matteness. Although the usage-amount is not specifically limited, Preferably it is 0.01-10 weight part with respect to 100 weight part of said copolymerization polyester resins, Preferably it is 0.01-5 weight part. If the amount is less than 0.01 parts by weight may have a problem that the desired effect is not properly expressed, when more than 10 parts by weight may be disadvantageous processing.

On the other hand, the method of mixing the copolymerized polyester resin and the inorganic additive described above in the present invention is not particularly limited, and, for example, according to one embodiment, the copolymerized polyester resin chip at a mixing ratio set when extruding the sheet. It is also possible to mix and use the inorganic additives directly to, or to prepare a mixed master batch of the copolymerized polyester resin and the inorganic additive according to another embodiment. In particular, when manufactured and used in a master batch, a molded article such as a sheet may be manufactured by (co) extrusion, (co) injection using 100% of the master batch, and a master batch and a pure copolymer polyester resin (i.e., Resin without an inorganic additive) can be mixed and used according to the desired degree of frost look. It is of course possible that further optionally available additives as described above can be added to the mixing master batch. For example, in the case of the matting agent masterbatch, it is preferably to be included as the outer surface layer of the molded sheet during coextrusion of the copolyester polyester resin composition of the present invention.

The copolymerized polyester resin composition of the present invention obtained as described above can be produced by various (co) injection or (co) extrusion molding according to the actual application purpose to produce a variety of molded products such as a single layer or a multilayered sheet.

For example, when the co-polyester resin composition of the present invention is mixed in a general sheet extruder, the sheet product is molded into a single layer structure. On the other hand, when using an extruder capable of making a multi-layered structure by co-extrusion, if necessary, only the outer surface layer of the molded article may be composed of the copolymerized polyester resin composition of the present invention.

The molded article of the present invention provided as described above preferably has a gloss of 30 or less, a haze of 50 to 95 and a transmittance of 50 to 95%. That is, the light reflection degree of the surface of the molded product is low and translucent, thereby providing a molded product having a high transparency while still serving to effectively mask the subject on the back of the molded product.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1

100 parts by weight of a copolymer polyester resin chip having an intrinsic viscosity of 0.78 dl / g (acid component: terephthalic acid, diol component: 60 mol% of 1,4-cyclohexanedimethanol + 40 mol% of ethylene glycol) and a particle size of 10 탆 A master batch was prepared by using a talc inorganic additive (35 parts by weight) and a montanic acid wax additive (1 part by weight) for improving flowability as a raw material, and used for extrusion. The copolyester resin was dried for 6 hours at 65 ℃ in a dehumidifying dryer before injection, the inorganic additive was used directly without a separate drying process. Immediately before extrusion, 10 parts by weight of the copolymerized polyester resin and the epoxy additive were mixed in a rotary stirrer and introduced into the extruder hopper. The extruder produced a sheet of 3 to 4 mm using a Breyer Sheet Extruder. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness was measured using a Gardner micro TRI gloss meter, and the gloss, haze, and transmittance were measured using a hazemeter of NIPPON DENSHOKU. It is shown in Table 1 below.

Example 2

Co-polyester resin (acid component: terephthalic acid, diol component: 60 mol% of 1,4-cyclohexanedimethanol + 40 mol of ethylene glycol) was used to prepare sheets of the same thickness using the same extruder as in Example 1. %) Uses inorganic additives (35 parts by weight) with an intrinsic viscosity of 0.78 dl / g and wax additives (1 part by weight) to improve flowability as raw materials to prepare and extrude master batches. Used for. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 3

Co-polyester resin (acid component: terephthalic acid, diol component: 1,4-cyclohexane dimethanol 60 mol% + ethylene glycol was used to produce sheets of the same thickness using the same extruder as in Example 1. 40 mole%) has an intrinsic viscosity of 0.78 dl / g, and has an inorganic additive (40 parts by weight) having a particle size of 10 μm in powder form and a stabilizer (0.5 parts by weight) for preventing phosphorus metal catalyst activity. It was prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 4

Co-polyester resin (acid component: terephthalic acid, diol component: 60 mol% of 1,4-cyclohexanedimethanol + 40 mol of ethylene glycol) was used to prepare sheets of the same thickness using the same extruder as in Example 1. %) Has an inherent viscosity of 0.78 dl / g and uses a inorganic additive (45 parts by weight) and wax additives (0.5 parts by weight) with a particle size of 10 μm in powder form to prepare a master batch with an inorganic additive for extrusion. It was. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 5

Co-polyester resin (acid component: terephthalic acid, diol component: 1,4-cyclohexane dimethanol 60 mol% + ethylene glycol was used to produce sheets of the same thickness using the same extruder as in Example 1. 40 mol%) has an intrinsic viscosity of 0.78 dl / g, and an inorganic additive (50 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) having an intrinsic particle size of 10 μm. The master batch was prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 6

Co-polyester resin (acid component: terephthalic acid, diol component: 60 mol% of 1,4-cyclohexanedimethanol + 40 mol of ethylene glycol) was used to prepare sheets of the same thickness using the same extruder as in Example 1. %) Has an intrinsic viscosity of 0.78 dl / g and an inorganic additive (50 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) together with an inorganic additive having a particle size of 5 μm in powder form. Master batches were prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 7

Co-polyester resin (acid component: terephthalic acid, diol component: 1,4-cyclohexane dimethanol 60 mol% + ethylene glycol was used to produce sheets of the same thickness using the same extruder as in Example 1. 40 mole%) has an intrinsic viscosity of 0.78 dl / g and an inorganic additive (50 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) having an particle size of 3 μm in powder form. The master batch was prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 8

Co-polyester resin (acid component: terephthalic acid, diol component: 60 mol% of 1,4-cyclohexanedimethanol + 40 mol of ethylene glycol) was used to prepare sheets of the same thickness using the same extruder as in Example 1. %) Has an intrinsic viscosity of 0.78 dl / g and an inorganic additive (50 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) with an inorganic additive having a particle size of 1 μm in powder form. Master batches were prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 1

Co-polyester resin (acid component: terephthalic acid, diol component: 1,4-cyclohexane dimethanol 60 mol% + ethylene glycol was used to produce sheets of the same thickness using the same extruder as in Example 1. 40 mol%) has an intrinsic viscosity of 0.78 dl / g, and an inorganic additive (10 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) having an intrinsic particle size of 10 μm. The master batch was prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 2

Co-polyester resin (acid component: terephthalic acid, diol component: 60 mol% of 1,4-cyclohexanedimethanol + 40 mol of ethylene glycol) was used to prepare sheets of the same thickness using the same extruder as in Example 1. %) Has an intrinsic viscosity of 0.78 dl / g and an inorganic additive (20 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) with an inorganic additive having a particle size of 10 μm in powder form. Master batches were prepared and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 3

Co-polyester resin (acid component: terephthalic acid, diol component: 1,4-cyclohexane dimethanol 60 mol% + ethylene glycol was used to produce sheets of the same thickness using the same extruder as in Example 1. 40 mole%) has an intrinsic viscosity of 0.78 dl / g and an acryl-based organic light diffuser (25 parts by weight), an antioxidant (0.3 parts by weight) and a wax additive (0.5 parts by weight) in a powder form having a particle size of 10 μm. Was prepared with the organic additives and used for extrusion. The cylinder temperature and die temperature of the extruder were set to 270 ° C, and the cooling roll temperature was set to 80 to 90 ° C. Surface roughness, glossiness, haze and permeability were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Glossiness Roughness (μm) Haze Permeability (%) Example 1 24 7 64.3 89.1 Example 2 19 8 70.2 85.2 Example 3 15 9 85 80 Example 4 13 10 88 72 Example 5 11 13 90 68 Example 6 13 11 89 67 Example 7 20 7 89 66 Example 8 25 5 90 68 Comparative Example 1 42 3 52.4 88.7 Comparative Example 2 32 2 63.7 88.1 Comparative Example 3 36 2 65 88.1

The sheet products molded by the methods of Examples 1 to 8 and Comparative Examples 1 to 3 had a translucent gray tone, but the surface state was different depending on the size and content of the inorganic material used. Comparative Example 1 prepared using a master batch having a low inorganic content significantly increased the gloss, compared with the other examples, haze was significantly reduced, transparency was increased. As shown in the Examples and Comparative Examples, the higher the inorganic content within a certain range, the lower the surface glossiness and the higher the haze. In addition, when comparing the surface roughness effect according to the inorganic particle size from Example 5 to 8, the smaller the inorganic particle size showed a softer surface.

As described above, according to the present invention can be used as a semi-transparent sheet for high-quality interior by reducing the transparency of the sheet as a main raw material without a separate coating process, by using an inorganic additive of a certain proportion and size The roughness can be adjusted. In addition, additives can be used through master batches to improve workability, such as eliminating dust problems. Furthermore, various master batches can be mixed and used to improve the surface of the sheet without developing new additives. Has the advantage of savings.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.

Claims (9)

(i) 100 parts by weight of copolymerized polyester resin having an intrinsic viscosity of 0.60 to 1.0 dl / g; And (ii) 30 to 60 parts by weight of an inorganic additive having a particle size of 2 to 50 µm; Co-polyester resin composition comprising a. The method of claim 1, wherein the (i) copolyester resin comprises a dicarboxylic acid component containing terephthalic acid, and 0.1 to 99.9 mol% of 1,4-cyclohexanedimethanol and 0.1 to 99.9 mol% of ethylene glycol. The copolymerization polyester resin composition characterized by carrying out esterification reaction and polycondensation reaction of the diol component containing. The copolymer polyester resin composition according to claim 2, wherein the diol component comprises 10 to 90 mol% of 1,4-cyclohexanedimethanol and 10 to 90 mol% of ethylene glycol. The copolymer polyester resin composition of claim 1, wherein the inorganic additive is selected from the group consisting of silica oxide, magnesium oxide, calcium carbonate, iron oxide, talc, and combinations thereof. The copolyester polyester composition of claim 1, wherein the copolyester resin composition further comprises an additive selected from the group consisting of phosphorus-based additives, waxes, antioxidants, inorganic matting agents, and combinations thereof. A molded article characterized in that the resin composition according to any one of claims 1 to 5 is formed by (co) injection or (co) extrusion molding. The molded article of claim 6, wherein the molded article has a gloss of 30 or less, a haze of 50 to 95, and a transmittance of 50 to 95%. The molded article of claim 6, wherein the molded article is a sheet having a single layer or a multilayer structure. The molded article according to claim 8, wherein when the molded article is a multi-layered sheet, the outer surface layer of the sheet is formed from the resin composition according to any one of claims 1 to 5.