JP2002194186A - Polyester resin decorative sheet, method for producing the decorative sheet, and container comprising the decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative polyester resin sheet having a beautiful design effect of an emboss-toned pattern or a frosted glass pattern which can be manufactured with a general-purpose production facility for a polyester resin sheet without using a device such as an embossing roller. SOLUTION: This decorative polyester resin sheet comprises (A) 20-95 wt.% of a polyethylene terephthalate-based resin having an inherent viscosity of 0.45-1.0 dl/g and (B) 5-80 wt.% of a branched polyethylene terephthalate-based copolymer resin in which, based on the whole constituents, 0.02-8 mol% of a compound having three or more carboxyl groups or/and hydroxyl groups in a molecule is copolymerized and which as an intrinsic viscosity of 0.6 dl/g and above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet made of a polyester resin having excellent design properties and a method for producing the same. More specifically, the present invention relates to a method for producing a decorative sheet made of a general-purpose polyester resin sheet without using a device such as an embossing roll. The present invention relates to a polyester resin decorative sheet having an embossed or frosted glass-like design, a method for producing the decorative sheet, and a container comprising the decorative sheet.

[0002]

2. Description of the Related Art Conventionally, thermoplastic polyester resins typified by polyethylene terephthalate resin have been noted for their excellent mechanical properties and chemical properties, and further excellent transparency and gas barrier properties in the field of fibers and films. From the viewpoint of safety and health, it is used in various fields including the food and beverage packaging field.

[0003] In recent years, transparent and highly safe and hygienic containers obtained by vacuum-forming or pressure-forming a melt-extruded unstretched transparent polyester resin sheet are remarkable as packaging materials for food and industry. It shows demand growth. In such fields, on the one hand, further improvement in physical and chemical properties such as heat resistance and solvent resistance, heat sealing properties, etc., on the other hand, sheets and the like imparting characteristic design properties etc. Containers are being demanded.

[0004] As a means for imparting a design property to a resin sheet, there is known a method of embossing (texturing). However, conventionally, in order to emboss a resin sheet, an embossing roll having an uneven surface is provided. There is a need for a molding method such as extruding using a sheet, extruding and casting after extruding a sheet or the like provided with unevenness, and softening and extruding the extruded sheet intermittently. For this reason, a complicated process such as a switching operation is required even when a dedicated molding machine is used or when a sheet is produced together with a smooth sheet.

[0005] Therefore, means for obtaining an embossed polyester resin decorative sheet only by switching the raw material resin while continuously operating the equipment, in other words, when the molten resin is released from the extruder to the free surface, the spontaneous Means for generating an embossed design have been demanded, but there has been no polyester resin that can achieve such a demand.

On the other hand, conventionally, attempts have been made to increase the melt viscosity of the resin by introducing branching into the molecular structure of the polyester resin and to improve the moldability in extrusion molding, blow molding and the like. However, simply extruding a polyester resin into which such a branching component has been introduced only produces irregular protrusions recognized as foreign substances, and cannot obtain a sheet with good design properties.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and therefore, the present invention can be manufactured by a general-purpose polyester resin sheet manufacturing apparatus without using an apparatus such as an embossing roll. An object of the present invention is to provide a decorative sheet made of a polyester resin having an embossed or frosted glass-like design, a method for producing the decorative sheet, and a container made of the decorative sheet.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above object can be achieved by forming a composition comprising a specific polyester resin. The finished product, that is, the invention of claims 1 to 7, has an intrinsic viscosity of 0.45 to 1.0 d.
1 / g polyethylene terephthalate resin (A)
20 to 95% by weight of a compound having three or more carboxyl groups and / or hydroxyl groups in the molecule is copolymerized in an amount of 0.02 to 8% by mole in all the constituents to have an intrinsic viscosity of 0.6 dl.
The present invention relates to a decorative sheet made of a polyester resin comprising 5 to 80% by weight of a branched copolymerized polyethylene terephthalate resin (B) having an intrinsic viscosity of 0.45 to 1 / g or more. 2.0 dl / g of polyethylene terephthalate resin (A) 20 to 95% by weight
And a compound having three or more carboxyl groups and / or hydroxyl groups in the molecule is 0.02 to 8 mol%
Branched copolymerized polyethylene terephthalate resin (B) having a copolymerized intrinsic viscosity of 0.6 dl / g or more.
80% by weight, and a method for producing a polyester resin decorative sheet which is extruded and molded.
The invention of No. 0 relates to a container formed by thermoforming the polyester resin decorative sheet according to any one of claims 1 to 7.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin decorative sheet of the present invention will be described in detail below. The polyethylene terephthalate-based resin (A), which is one of the raw materials constituting the present invention, is a polyethylene terephthalate-based resin having terephthalic acid or a derivative thereof as a dicarboxylic acid component and ethylene glycol as a diol component as a main component, 25 mol% or less, preferably 2 mol% of all components
In a range of 0 mol% or less, more preferably 15 mol% or less, a component other than terephthalic acid or a derivative thereof and ethylene glycol may be copolymerized.
However, compounds having three or more carboxyl groups and / or hydroxyl groups in the molecule are excluded. The derivative means an alkyl ester having about 1 to 4 carbon atoms.

[0010] Transparency, flexibility, impact resistance, and the like tend to be imparted by copolymerizing components other than terephthalic acid or a derivative thereof and ethylene glycol at 25 mol% or less. On the other hand, when it exceeds 25 mol%, the polymerizability of the polyethylene terephthalate resin (A) is deteriorated, so that the mechanical strength and the weather resistance tend to be inferior. Specific examples of the dicarboxylic acid component other than terephthalic acid or a derivative thereof include, for example, isophthalic acid, phthalic acid, phenylenedioxydiacetic acid, 4,4′-diphenyldicarboxylic acid, and 4,4′-diphenoxyethanedicarboxylic acid. Acid, 4,
Aromatic dicarboxylic acids such as 4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl sulfone dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid and the like, and esters of these alkyl esters having about 1 to 4 carbon atoms such as alkyl esters Forming derivatives.

Among them, isophthalic acid, 2,6-naphthalenedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid are preferably used. By copolymerizing these, the crystallinity can be reduced without impairing the mechanical strength, so that a polyester resin decorative sheet having good transparency can be produced. As the diol component other than ethylene glycol, specifically, for example,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 10-decanediol, 2,2-dimethyl-1,3-propanediol,
Aliphatic diols such as diethylene glycol, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
Alicyclic diols such as 1,4-cyclohexanedimethanol, 1,2-cyclohexanediol and 1,4-cyclohexanediol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, Aromatic diols such as 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and bis (4-β-hydroxyethoxyphenyl) sulfonic acid are exemplified.

Among them, 1,4-butanediol, 1,4-
Cyclohexanedimethanol and diethylene glycol are preferably used. By copolymerizing these,
Since the crystallinity can be reduced without impairing the mechanical strength, a polyester resin decorative sheet having good transparency can be manufactured. Further, for example, hydroxycarboxylic acids and alkoxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, and stearic acid, stearyl alcohol, benzyl alcohol, benzoic acid, t-butylbenzoic acid Monofunctional components such as benzoylbenzoic acid and the like may be copolymerized.

Further, as the polyethylene terephthalate resin (A) component in the present invention, a polyalkylene ether glycol may be copolymerized in the polyethylene terephthalate resin at 10% by weight or less. By copolymerizing the polyalkylene ether glycol at a content within the above range, flexibility can be imparted to the polyester resin decorative sheet of the present invention.
If the amount is more than 10% by weight, the transparency of the polyester resin decorative sheet tends to deteriorate.

Specific examples of the polyalkylene ether glycol include polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, and polytetramethylene ether glycol, among which polytetramethylene ether glycol is flexible. Particularly preferred from the viewpoint of application. The polyalkylene ether glycol has a number average molecular weight of 400.
It is preferably from 4,000 to 4,000, more preferably from 500 to 2,000, and particularly preferably from 600 to 1,500. If the number average molecular weight is less than 400, the effect of imparting flexibility tends to be insufficient, while if it exceeds 4000, the polymerizability tends to decrease.

In the present invention, the polyethylene terephthalate-based resin (A) is basically a conventional polyester resin comprising a dicarboxylic acid component containing terephthalic acid or a derivative thereof as a main component and a diol component containing ethylene glycol as a main component. It is manufactured by the manufacturing method of That is, a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing ethylene glycol as a main component are esterified in an esterification reaction tank, and the obtained esterification reaction product is transferred to a polycondensation reaction tank and subjected to polycondensation. A transesterification reaction, a transesterification reaction of a dicarboxylic acid component containing an ester-forming derivative of terephthalic acid as a main component and a diol component containing ethylene glycol as a main component in an esterification reaction tank, and the resulting transesterification reaction product Is transferred to a polycondensation reaction tank and subjected to polycondensation, or a slurry prepared by dispersing a dicarboxylic acid component containing terephthalic acid as a main component in a diol component containing ethylene glycol as a main component in a slurry preparation tank. , An esterification reaction product or a transesterification reaction product obtained above in an esterification reaction tank , Esterified added continuously, may also take any of such continuous direct polymerization method polycondensation by transferring the reaction product obtained continuously or / and stepwise polycondensation reaction tank.

In general, the resin obtained by the polycondensation reaction is drawn out in a strand form from a discharge port provided at the bottom of the polycondensation reaction tank, and cut with a cutter with or after cooling with water, and then pelletized by a cutter. However, by heating the pellets after the polycondensation and subjecting them to solid-phase polymerization, the degree of polymerization can be further increased, and acetaldehyde and low-molecular-weight oligomers as reaction by-products can be reduced. it can.

In the above-mentioned production method, the esterification reaction may be carried out, if necessary, for example, by using diantimony trioxide,
In the presence of an esterification catalyst such as an organic acid salt such as antimony, titanium, magnesium and calcium, 200 to 27
The reaction is carried out at a temperature of about 0 ° C. and a pressure of about 1 × 10 ⁵ to 4 × 10 ⁵ Pa, and the transesterification reaction may be performed, for example, as required, for example, lithium, sodium, potassium, magnesium, calcium, manganese, titanium and zinc. 200-270 ° C in the presence of a transesterification catalyst such as an organic acid salt such as
The temperature is about 1 × 10 ⁵ to 4 × 10 ⁵ Pa.

The polycondensation reaction is carried out, for example, in the presence of orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and phosphorus compounds such as esters and organic acid salts thereof, and, for example, diantimony trioxide, Metal oxides such as germanium dioxide and germanium tetroxide, or antimony, germanium,
In the presence of a polycondensation catalyst such as an organic acid salt such as zinc, titanium and cobalt, a temperature of about 240 to 290 ° C. and 1 × 10 ²
It is performed under reduced pressure of about 2 × 10 ³ Pa.

In the solid-state polymerization, after pre-crystallization is performed by heating at a temperature of about 120 to 200 ° C. for 1 minute or more, a temperature of about 180 to 240 ° C. and an inert gas such as nitrogen gas are used. Under atmosphere and / or 1 × 10 ² to 2 × 10 ³
It is performed under reduced pressure of about Pa. Next, the branched copolymerized polyethylene terephthalate resin (B), which is another raw material constituting the present invention, substantially contains terephthalic acid or a derivative thereof as a dicarboxylic acid component, and ethylene glycol as a diol component. A polyethylene terephthalate resin in which a compound having three or more carboxyl groups and / or hydroxyl groups in the molecule is copolymerized.

In the molecule, three or more carboxyl groups and / or
And the content of the compound having a hydroxyl group is usually from 0.02 to 8 assuming that the total sum of all dicarboxylic acid components and all diol components constituting the branched copolymerized polyethylene terephthalate resin (B) is 100 mol%. Mol%, preferably 0.05 to 5 mol%, particularly preferably 0.1 to 2 mol%, more preferably 0.3 to 1 mol%. If the content of the compound having three or more carboxyl groups and / or hydroxyl groups in the molecule is less than 0.02 mol%, it is difficult to express the design of the decorative sheet in a satisfactory manner, which is not preferable. %, It is not preferred because not only the polycondensation itself becomes difficult but also it becomes difficult to melt-extrude the polyester resin decorative sheet.

The compound having three or more carboxyl groups and / or hydroxyl groups in the molecule used in the branched copolymerized polyethylene terephthalate resin (B) constituting the present invention includes three or more carboxyl groups in the molecule. Although it is not limited as long as it is a compound having a group or / and a hydroxyl group, specifically, for example, tricarballylic acid, hexanetricarboxylic acid, trimellitic acid, trimesic acid,
Polyfunctional carboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, naphthalenetetracarboxylic acid, gallic acid, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, 1,2,6-
Hexanetriol, sorbital, 1,1,4,4-
Polyfunctional alcohols such as tetrakis (hydroxymethyl) cyclohexane, dipentaerythritol, polyglycerol (compounds in which glycerol is condensed about 2 to 20 and mixtures thereof), and polyols (compounds in which alkylene oxides having about 2 to 4 carbon atoms are condensed) And the like. In addition, you may use these compounds in combination of 2 or more types. Further, the carboxylic acid in these compounds may be, for example, an ester-forming derivative such as an alkyl ester thereof having about 1 to 4 carbon atoms, or an acid anhydride at the stage of the raw material before being copolymerized. .

Among them, trimellitic acid, pyromellitic acid, glycerol, trimethylolpropane, pentaerythritol, polyglycerol, and polyol are preferable from the viewpoint of the appearance of design as a decorative sheet. Further, in addition to the compound having three or more carboxyl groups and / or hydroxyl groups in the molecule, a polyfunctional epoxy compound, a polyfunctional isocyanate compound, a polyfunctional oxazoline compound, and the like, as long as the effects of the present invention are not impaired. One or more of other branching components may be used in combination.

The branched copolymerized polyethylene terephthalate resin (B) in the present invention contains terephthalic acid or a derivative thereof as a dicarboxylic acid component, ethylene glycol as a diol component, and contains three or more carboxyl groups or As long as the compound having a hydroxyl group is copolymerized with 0.02 to 8 mol%, components other than terephthalic acid or a derivative thereof and ethylene glycol may be further copolymerized. The same ones as described in the polyethylene terephthalate resin (A) can be used.

These copolymer components are used in an amount of not more than 25 mol%, preferably not more than 20 mol%, more preferably not more than 15 mol% of all the components constituting the branched copolymerized polyethylene terephthalate resin (B). Can be When such a copolymer component is copolymerized at 25 mol% or less, transparency tends to be improved and flexibility tends to be imparted. On the other hand, if it exceeds 25 mol%, the polymerizability of the branched copolymerized polyethylene terephthalate-based resin (B) is deteriorated, and as a result, the mechanical strength and heat resistance tend to be inferior.

In the present invention, the branched copolymerized polyethylene terephthalate-based resin (B) can be produced basically by the same production method as described for the polyethylene terephthalate-based resin (A). in this case,
Usually, three or more carboxyl groups and / or
And a compound having a hydroxyl group may be added simultaneously with a dicarboxylic acid component such as terephthalic acid or a derivative thereof, and a diol component such as ethylene glycol.However, a polycondensation reaction is performed on an esterification reaction product or a transesterification reaction product. After being transferred to the tank, it can be added at the stage of polycondensation.

In the present invention, the branched copolymerized polyethylene terephthalate-based resin (B) is a polyethylene terephthalate in which the compound having at least three carboxyl groups and / or hydroxyl groups in the molecule is not copolymerized. After the polyethylene resin is produced, the polyethylene terephthalate resin and a compound having three or more carboxyl groups and / or hydroxyl groups in a molecule are melt-kneaded with an extruder or the like, thereby producing the resin by a transesterification reaction. Can also. When produced only by polycondensation, the resulting branched copolymerized polyethylene terephthalate-based resin (B)
In some cases, extraction is difficult because the melt viscosity is too high, or deterioration may be accelerated because extraction takes a long time. In such a case, it is preferable to manufacture by melt-kneading.

When the branched copolymerized polyethylene terephthalate resin (B) is produced by the above-mentioned melt-kneading,
An extruder or a continuous horizontal reactor having no forced conveying force is suitably used, and preferably 180 to 320
C., more preferably at a temperature of 220 to 280C. Among them, a twin-screw extruder is preferably used. In the case of the above-mentioned melt-kneading, the polyethylene terephthalate-based resin in which the compound having three or more carboxyl groups or / and hydroxyl groups in the molecule is not copolymerized is preferably dried and put in advance. 400 moisture content
ppm or less, preferably 200 ppm or less, particularly preferably 50 ppm or less. By drying in this manner, deterioration and coloring of the branched copolymerized polyethylene terephthalate resin (B) are suppressed, and the transesterification reactivity of the compound having three or more carboxyl groups and / or hydroxyl groups in the molecule is reduced. Can be enhanced.

Further, in order to suppress the deterioration, coloring, foaming, etc. of the resin during melt-kneading, and to remove by-products and the like generated by kneading, a melt-kneading apparatus may be used instead of or in combination with the drying. It is preferable to set the pressure of the molten resin staying portion in the inside to a reduced pressure state, the pressure is particularly preferably 2 × 10 ⁴ Pa or less, and more preferably 3 × 10 ³ Pa or less.

However, when the compound having three or more carboxyl groups and / or hydroxyl groups in the molecule is distilled off from the melt-kneading apparatus by reducing the pressure, the degree of pressure reduction is suppressed. Alternatively, it is preferable not to reduce the pressure. Further, after the above-mentioned melt-kneaded product is made into a solid state, it is possible to produce a branched copolymerized polyethylene terephthalate-based resin (B) having a higher melt viscosity by subsequently performing heat treatment or solid-phase polycondensation. .

In the present invention, the polyethylene terephthalate-based resin (A) and the branched copolymerized polyethylene terephthalate-based resin (B) may be obtained by using the raw materials produced by polycondensation or melt kneading as described above. Scraps generated in the process of molding these resins into molded articles, or pulverized products collected from the market can also be used. These can be used as raw materials in the form of pellets or the like, once melted or crushed products can be used as raw materials as they are.

The polyester resin decorative sheet of the present invention may contain fine particles, other thermoplastic resins and thermoplastic elastomers, additives, reinforcing materials, and the like, as long as the effects of the present invention are not impaired. Here, as the fine particles,
For example, silica, alumina, titania, kaolin, clay, calcium carbonate, calcium phosphate, lithium fluoride,
Examples thereof include inorganic fine particles such as carbon black, precipitated fine particles resulting from a catalyst such as an alkali metal or alkaline earth metal and a phosphorus compound during polymerization of polyester, and organic fine particles such as various crosslinked polymers. Further, as other thermoplastic resins and thermoplastic elastomers, for example, polyethylene, polypropylene, and their maleic anhydride modified products, polyolefin resins such as ionomers, polyamide resins,
Polycarbonate resins and polystyrene resins are exemplified. Further, as additives and reinforcing agents, for example, hindered phenol-based, phosphite-based, thioether-based antioxidants, benzotriazole-based, benzophenone-based, benzoate-based, hindered amine-based,
Light stabilizers such as cyanoacrylates, crystal nucleating agents, molecular weight regulators, hydrolysis stabilizers, antistatic agents, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, foaming agents, antibacterial agents, coloring Additives such as an agent and a dispersing aid, and reinforcing materials such as glass fiber, carbon fiber, mica, and potassium titanate.

As an addition method, usually, the polyethylene terephthalate-based resin (A) and / or the branched copolymerized polyethylene terephthalate-based resin (B) are used while being added. As for those, in addition to being contained in the polycondensation process, they can be contained later in the resin produced once by melt kneading, etc.
It may be added at the time of compounding the raw materials before producing the polyester resin decorative sheet.

The polyethylene terephthalate resin (A) in the present invention has an intrinsic viscosity of phenol / 1,1,2,2-tetrachloroethane (weight ratio = 1/1) in terms of mechanical strength and the like. The value measured at 30 ° C. in the solvent is 0.45 to 1.0 dl / g,
0.9 dl / g, preferably 0.6 to 0.8 dl / g.
More preferably, it is dl / g. 0.45 intrinsic viscosity
If it is less than dl / g, the mechanical strength of the obtained polyester resin decorative sheet is inferior, and if it exceeds 1.0 dl / g, it is difficult to exhibit the design as the polyester resin decorative sheet of the present invention. Therefore, it is not preferable.

The intrinsic viscosity of the branched copolymerized polyethylene terephthalate resin (B) is determined by the same method as that for the polyethylene terephthalate resin (A).
It is 6 dl / g or more, preferably 0.8 dl / g or more, more preferably 1.0 dl / g or more. Furthermore, when the branched copolymerized polyethylene terephthalate-based resin (B) is dissolved in a mixed solvent to measure the intrinsic viscosity, the resin may be too high in intrinsic viscosity to be insoluble. If the intrinsic viscosity is less than 0.6 dl / g, it is not preferable because it becomes difficult to exhibit the design properties as the polyester resin decorative sheet of the present invention.

The branched copolymerized polyethylene terephthalate resin (B) in the present invention has a melt viscosity of 1000 Pa · s or more measured at a temperature of 280 ° C. and a shear rate of 100 sec ⁻¹ according to JIS K7199. More preferably, it is more preferably 2000 Pa · s or more.
It is particularly preferred that the pressure be 000 Pa · s or more. When the melt viscosity is less than 1000 Pa · s, the melt viscosity is low, so that it tends to be difficult to express the design as a decorative sheet.

Further, the melt viscosity of the branched copolymerized polyethylene terephthalate resin (B) measured at a temperature of 280 ° C. and a shear rate of 100 sec ^-1 according to JIS K7199 was measured in the same manner. The value divided by the melt viscosity of A) is preferably 3.0 or more, more preferably 4.0 or more,
It is particularly preferred that it is 5.0 or more. If it is less than 3.0, the design as a decorative sheet tends not to be exhibited because the melt viscosity is low.

The raw material of the polyester resin decorative sheet of the present invention is polyethylene terephthalate resin (A) 20
And a branched copolymer polyethylene terephthalate-based resin (B) comprising 30 to 92% by weight of a branched copolymerized polyethylene terephthalate-based resin (B). 8
The content of the polyethylene terephthalate resin (A) is preferably 40 to 90% by weight, and the content of the branched copolymerized polyethylene terephthalate resin (B) is 10 to 6%.
Particularly preferred is 0% by weight.

The decorative sheet made of the polyester resin of the present invention exhibits good design as a decorative sheet even when the content of the polyethylene terephthalate resin (A) is less than 20% by weight or more than 95% by weight. I can't do it. The polyester resin decorative sheet of the present invention having the above-described structure has irregularities on one or both surfaces of the sheet and has an embossed three-dimensional appearance, in other words, a sheet having a fogged glass-like pattern. It is.
The frosted glass tone is a form that is transparent but cannot be read at a certain distance when characters or the like are viewed through the decorative sheet, depending on the size of the characters.

Further, in the decorative sheet made of a polyester resin of the present invention, the haze measured according to JIS K7105 is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less. Is particularly preferred. When the haze of the polyester resin decorative sheet is 15% or less, not only the design of the polyester resin decorative sheet of the present invention is good, but also in the case of a container, it becomes easy to confirm the presence of the contents, If it is the same as the exhibition,
This is preferable because it is possible to confirm the presence of an object to be displayed.

The decorative sheet made of the polyester resin of the present invention may have any thickness as long as the decorative sheet has the above-mentioned embossed three-dimensional appearance, but in order to exhibit good design properties as a decorative sheet, 0.1 to 10 mm is preferred. Further, the thickness can be appropriately selected and used depending on the intended use. Specifically, for example, when it is subjected to vacuum forming, pressure forming, or the like, the thickness is preferably 0.2 to 1 mm, more preferably 0.4 to 0.8 mm. In the case where the sheet material is directly cut and used, the thickness is preferably 0.6 to 6 mm, and 0.8 to 4 m.
m is more preferable. When used for a synthetic skin material or the like, it is preferably 0.5 to 2.5 mm,
More preferably, it is 0.8 to 1.5 mm.

A measuring instrument such as a micrometer or a caliper can be used for the thickness measurement. Since the decorative sheet made of the polyester resin of the present invention has emboss-like irregularities and is not uniform in thickness finely, the thickness is at least 0.1 mm.
It is a value measured so that a plane portion of 3 cm ² hits the sheet surface. In an automatic measuring device using a laser beam or the like, the thickness of the polyester resin decorative sheet of the present invention is:
Measurement may not be accurate.

The decorative sheet made of the polyester resin of the present invention has an intrinsic viscosity of 0.4 to 0.4 as measured by the same method as described above.
It is preferably 1.2 dl / g, and 0.5 to 0.9 d.
1 / g, more preferably 0.6 to 0.8 dl /
g is particularly preferred. 0.4 dl / g intrinsic viscosity
If it is less than 1, the mechanical strength of the sheet tends to be inferior, while if it exceeds 1.2 dl / g, the formability in forming the sheet tends to be inferior. Hereinafter, a method for producing the polyester resin decorative sheet of the present invention will be described. The polyester resin decorative sheet of the present invention comprises, as raw materials, a polyethylene terephthalate-based resin (A) and a branched copolymerized polyethylene terephthalate-based resin (B). After adding and compounding a resin, a thermoplastic elastomer, an additive, a reinforcing material, and the like, the mixture is usually mixed at a temperature of 180 to 320 ° C., preferably 220 to 280 using a melt-kneading apparatus such as a single-screw or twin-screw extruder.
It is manufactured by melt-kneading at a temperature of ° C. and extruding from a die.

At this time, each resin as a raw material is preferably dried beforehand in order to suppress deterioration, coloring, foaming, etc. of the obtained polyester resin decorative sheet, and the water content thereof is 400 ppm or less. And more preferably 200 ppm or less.
pm or less is particularly preferred. Further, in order to suppress the deterioration, coloring, foaming, and the like of the resin during melt-kneading, and to remove by-products and the like generated by kneading, instead of or in addition to the drying, the melting in the melt-kneading apparatus is performed. It is preferable to reduce the pressure in the resin retaining section, and it is preferable that the pressure be 2 × 10 ⁴ Pa or less, and 3 × 10 ³ Pa
It is more preferable to set the following. When the pressure inside the molding machine is reduced as described above, it is particularly preferable to use a twin-screw extruder.

The residence time of the melt-kneading is preferably 0.5 to 20 minutes, more preferably 0.8 to 10 minutes, particularly preferably 1 to 8 minutes. If the time is less than 0.5 minute, the mixing of the polyethylene terephthalate resin (A) and the branched copolymerized polyethylene terephthalate resin (B) is insufficient, so that the mechanical properties and transparency of the polyester resin decorative sheet tend to be inferior. On the other hand, if it exceeds 20 minutes, the expression of the design as a decorative sheet tends to be insufficient. Here, the residence time refers to the time from the introduction of the raw material into the melt kneading apparatus until the raw material is extruded from the die.

Further, one of the polyethylene terephthalate resin (A) and the branched copolymerized polyethylene terephthalate resin (B) is charged from a raw material inlet of an extruder, and after melting, the other component is added. It can also be added and extruded from the middle of the extruder. When the shear rate of the extruder is high, the transesterification reaction proceeds when both raw materials are charged at the same time, and as a result, the decorative sheet may not have good design properties. On the other hand, when one resin is added in the middle, the embossed design property may be improved. Examples of the method of the addition in the middle include a method of adding from a side feeder provided in the middle of the barrel of the extruder. In addition, the measurement of the residence time when one resin is added in the middle is defined as the time from the introduction of the raw material by the middle addition to the extrusion of the resin from the die.

The shape of the die at the time of extrusion molding is arbitrary. When the die is extruded into a flat sheet using a flat die, a T die, a rectangular die, or the like, or extruded into a tubular shape using a circular die, this is cut open. To form a flat sheet. When molding into a flat sheet using a T-die or the like, the molten resin extruded from the die is usually 1
It is obtained by bringing it into close contact with a cooling roll set at 0 to 80 ° C. and solidifying it. It is particularly preferable that the method of bringing the molten resin into contact with the cooling roll, which comes into contact first, by the electrostatic contact method in order to produce the polyester resin decorative sheet of the present invention. When a method such as sandwiching with a plurality of rolls is used instead of the electrostatic adhesion method, the design property as a decorative sheet may not be sufficiently exhibited.

The decorative sheet made of a polyester resin of the present invention can be used as a laminate by producing the above-mentioned extrusion by coextrusion or by adding a process such as laminating or laminating to the decorative sheet. it can. Further, the surface layer can be coated and used by applying and drying a solution in which a resin or the like is dissolved or suspended in water or an organic solvent. Additives such as antioxidants, light stabilizers, antistatic agents, lubricants, plasticizers, flame retardants, flame retardant auxiliaries, antibacterial agents, colorants, etc. Or a reinforcing material may be contained.

These lamination and coating can be used in combination, and either one side or both sides of the polyester resin decorative sheet of the present invention may be used. By applying such lamination and / or coating, the decorative sheet has improved weather resistance, anti-fogging property, flexibility, flame retardancy, scratch resistance, moldability, etc. In some cases, a decorative sheet having good properties may be obtained.

The decorative sheet made of the polyester resin obtained by the present invention can be manufactured into trays, containers, three-dimensional objects, etc. having excellent design properties by performing thermoforming such as vacuum forming and pressure forming. When a polyester resin decorative sheet is subjected to thermoforming, the thickness is usually 0.2 to 1 mm.
Is obtained by heating the decorative sheet made of polyester resin of the above to a surface temperature at which the shaping can be carried out at about 80 to 120 ° C., and bringing the decorative sheet into close contact with a vacuum or / and a pressure forming mold. There is no limitation as to which side of the sheet is to be in close contact with the mold, and a match mold or plug assist can be used. It is preferable to perform vacuum forming as a surface to be formed from the viewpoint of developing design properties as a thermoformed product.

The decorative sheet made of polyester resin of the present invention not only has excellent design properties as a decorative sheet, such as having a three-dimensional effect, but also has effects such as inconspicuous scratches, and moderate scattering of reflected light and transmitted light. Therefore, for example, squeezed containers for food and drink or industrial use, carports and temporary houses as glass substitutes, building materials for indoor use, interior materials for product displays and displays, miscellaneous goods such as lighting covers and bulletin boards And the like.

[0051]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to the following Examples without departing from the scope of the invention. The resins used in Examples and Comparative Examples are shown below. The composition of each resin was analyzed by proton NMR (however, only polyfunctional carboxylic acid components were analyzed by pyrolysis gas chromatography).
Melt viscosity was measured at a temperature of 28 according to JIS K7199.
It is a value measured at 0 ° C. and a shear rate of 100 sec ⁻¹ .

A-1: produced by a direct polycondensation reaction,
50.0 mol% of terephthalic acid, ethylene glycol 4
A polyethylene terephthalate-based resin composed of 8.6 mol% and 1.4 mol% of diethylene glycol (having an intrinsic viscosity of 0.4%).
71 dl / g, melt viscosity 500 Pa · s). A-2: 45.2 mol% of terephthalic acid, 4.8 mol% of isophthalic acid, 48.7 mol% of ethylene glycol, diethylene glycol 1.
3 mol% polyethylene terephthalate resin (intrinsic viscosity 0.65 dl / g, melt viscosity 350 Pa.
s).

A-3: 50.0 mol% of terephthalic acid, 34.8 mol% of ethylene glycol, 15.2 mol% of cyclohexanedimethanol, 1.7 of diethylene glycol produced by a polycondensation reaction following the transesterification reaction.
Mol% copolymerized polyethylene terephthalate resin (intrinsic viscosity 0.68 dl / g, melt viscosity 400 Pa.
s).

A-4 (for Comparative Example); terephthalic acid 5 produced by a solid polycondensation reaction following a direct polycondensation reaction
Polyethylene terephthalate resin (intrinsic viscosity 1.1 dl / g, melt viscosity 3100 Pa · s) composed of 0.0 mol%, 49.2 mol% of ethylene glycol and 0.8 mol% of diethylene glycol. A-5 (for comparative example); produced by a direct polycondensation reaction,
50.0 mol% of terephthalic acid, ethylene glycol 4
A polyethylene terephthalate-based resin composed of 9.1 mol% and 0.9 mol% of diethylene glycol (having an intrinsic viscosity of 0.1 mol%).
Since it was 41 dl / g and the melt viscosity was low, it could not be measured under the same conditions as other resins.)

B-1: produced by a direct polycondensation reaction,
50.0 mol% of terephthalic acid, ethylene glycol 4
Branched copolymerized polyethylene terephthalate-based resin (intrinsic viscosity 1.15) composed of 8.7 mol%, pentaerythritol 0.2 mol%, and diethylene glycol 1.1 mol%
dl / g, melt viscosity 3500 Pa · s). B-2: Produced by melt-kneading A-1 and pentaerythritol at 280 ° C. using a twin-screw extruder and further subjecting the kneaded product to a solid-state polycondensation reaction at 220 ° C. for 20 hours under nitrogen. Branched copolymer polyethylene terephthalate resin (intrinsic viscosity 1.6 dl / g) composed of 50.0 mol% of terephthalic acid, 48.5 mol% of ethylene glycol, 0.2 mol% of pentaerythritol and 1.3 mol% of diethylene glycol , Melt viscosity 8500Pa ・
s).

B-3: A-1 and pyromellitic anhydride are melt-kneaded at 280 ° C. using a twin screw extruder, and the kneaded product is subjected to a solid-state polycondensation reaction at 220 ° C. for 25 hours under nitrogen. 49.7 mol% of terephthalic acid,
Pyromellitic acid 0.3 mol%, ethylene glycol 48.
A branched copolymerized polyethylene terephthalate-based resin composed of 7 mol% and 1.3 mol% of diethylene glycol (intrinsic viscosity: 1.4 dl / g, melt viscosity: 6,200 Pa · s).

B-4 (for Comparative Example); 49.7 mol% of terephthalic acid and 0 of pyromellitic acid produced by melt-kneading A-1 and pyromellitic anhydride at 280 ° C. using a twin screw extruder. 0.3 mol%, ethylene glycol 4
Branched copolymerized polyethylene terephthalate-based resin composed of 8.7 mol% and diethylene glycol 1.3 mol% (intrinsic viscosity 0.55 dl / g, melt viscosity 170 Pa ·
s).

C-1 (for Comparative Example); polybutylene terephthalate resin (Novadur 5010 manufactured by Mitsubishi Engineering-Plastics Corporation, intrinsic viscosity 1.1 dl / g, melt viscosity 200 Pa · s) C-2 (for Comparative Example); ester 50.0 mol% of 2,6-naphthalenedicarboxylic acid, 48.7 mol% of ethylene glycol, produced by a polycondensation reaction following the exchange reaction,
Polyethylene naphthalate resin composed of 1.3 mol% of diethylene glycol (intrinsic viscosity: 0.60 dl / g, melt viscosity: 1,400 Pa · s).

Examples 1 to 4 and Comparative Examples 1 to 8 Two types of resins shown in Table 1 were mixed with a twin screw film extruder ("BT-30" manufactured by Plastic Engineering Laboratory Co., Ltd.) equipped with a T die. ) At a temperature of 280 ° C., 1 × 1
After being melt-extruded into a sheet under a reduced pressure of 0 ² Pa, an unstretched film having a thickness of 600 μm was formed by being fastened to a cooling roll set at a surface temperature of 40 ° C. by being provided with an electrostatic adhesion device and rapidly cooled. .

The resulting sheet was evaluated for intrinsic viscosity, sheet appearance, character legible distance, haze and elongation at break in the following manner, and the results are shown in Table 1. About 0.25 g of intrinsic viscosity sample (resin pellet or sheet)
After dissolving in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio = 1/1) at 110 ° C. in about 25 cm ³ , the solution was cooled to 30 ° C., and a fully automatic solution viscometer (Chuo Rikasha Co., Ltd.) "2CH type DJ504") at 30 ° C.

Sheet appearance (embossed tone) The appearance of the sheet was visually observed and judged according to the following criteria. -Those that have obvious surface irregularities and can be judged to be embossed: ○-Surfaces have irregularities but cannot be judged to be embossed: △-Those that have no surface irregularities: × Legs readable distance A4 A document is created on the paper surface with 10 Mincho fonts, and an A4-size decorative sheet is placed in parallel with this at an interval of 30 cm, and the sheet is placed 15 cm away from the sheet surface in the vertical direction (eye position). Confirmed the document through. The distance between the paper and the sheet is 30cm to 25, 20, 15, 1
When approaching 0, 5, and 2 cm, the distance at which characters became legible was measured. In this measurement, when the distance between the sheet and the sheet was set to 0 (contacted), it was assumed that the sheet could read characters. At this time, a sheet in which characters could not be read was evaluated as x.

The haze was measured according to JIS K7105. In the appearance of the sheet, an apparently opaque one was not measured, and was indicated by x. In accordance with JIS K7127, the sheet was punched out into a No. 2 type test piece so that the extrusion direction became the tensile direction, and
Tested at 0 mm / min. The evaluation of the elongation at break was based on the marked line based on the parallel portion 20 mm of the dumbbell piece.

Example 5 The resin of A-1 was applied to a twin-screw film forming machine equipped with a T die (“BT-3” manufactured by Plastic Engineering Laboratory Co., Ltd.).
0 "), and the resin of B-1 is supplied from a side feeder connected in the middle of the barrel of the extruder.
After being melt-extruded into a sheet under a reduced pressure of 1 × 10 ² Pa at a temperature of 1 × 10 ² Pa, the sheet is provided with an electrostatic adhesion device and is brought into close contact with a cooling roll set at a surface temperature of 40 ° C. to be rapidly cooled to a thickness of 60 ° C.
A 0 μm unstretched film was formed.

With respect to the obtained sheet, the intrinsic viscosity, the sheet appearance, the haze, the legible distance of characters and the elongation at break were evaluated by the above-mentioned methods, and the results are shown in Table 1.

[0065]

[Table 1]

[0066]

According to the present invention, there is provided a polyester resin having a clean embossed or frosted glass-like design which can be easily manufactured by a general-purpose polyester resin sheet manufacturing apparatus without using an apparatus such as an embossing roll. A decorative sheet can be provided and a method for producing the same can be provided, and its industrial value is remarkable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 67:00 B29K 67:00 B29L 7:00 B29L 7:00 F term (Reference) 3E086 AB01 BA02 BA15 BA35 BB01 BB61 CA01 CA11 DA08 4F071 AA43 AA46 AA88 AF43 BB06 BC01 BC12 4F207 AA24E AB11 AB16 AF01 AF04 AG01 AH55 AH56 AH58 AL10 KA01 KA17 KF01 KF12 KK13 KL84 4J002 CF01X CF06W GL00

Claims (10)

[Claims] 1. A polyethylene terephthalate resin (A) having an intrinsic viscosity of 0.45 to 1.0 dl / g.
5% by weight and a compound having three or more carboxyl groups and / or hydroxyl groups in the molecule contain 0.02 to
A decorative sheet made of a polyester resin, comprising 5 to 80% by weight of a branched copolymerized polyethylene terephthalate resin (B) having an intrinsic viscosity of 0.6 dl / g or more copolymerized by 8 mol%. 2. A branched copolymerized polyethylene terephthalate resin (B) having a temperature of 280 ° C. and a shear rate of 100 sec.
The polyester resin decorative sheet according to claim ^1, wherein the melt viscosity at ^-1 is 1000 Pa · s or more. 3. The value obtained by dividing the melt viscosity of the branched copolymerized polyethylene terephthalate resin (B) by the melt viscosity of the polyethylene terephthalate resin (A) at a temperature of 280 ° C. and a shear rate of 100 sec ⁻¹ is 3.0 or more. The polyester resin decorative sheet according to claim 1 or 2, wherein: 4. The polyethylene terephthalate-based resin (A) and / or the branched copolymerized polyethylene terephthalate-based resin (B) accounts for not more than 25 mol% of all constituent components, and is isophthalic acid or a derivative thereof and / or naphthalenedicarboxylic acid. 4. The polyester resin decorative sheet according to claim 1, wherein a derivative thereof is copolymerized. 5. The polyethylene terephthalate-based resin (A) and / or the branched copolymerized polyethylene terephthalate-based resin (B) account for not more than 25 mol% of all the constituent components in 1,4-butanediol, cyclohexanedimethanol and diethylene glycol. At least one selected from
The polyester resin decorative sheet according to any one of claims 1 to 4, wherein the above components are copolymerized. 6. The polyester resin decorative sheet according to claim 1, wherein the decorative sheet has a thickness of 0.1 to 10 mm. 7. The polyester resin decorative sheet according to claim 1, wherein a haze measured according to JIS K7105 is 15% or less. 8. A polyethylene terephthalate-based resin (A) having an intrinsic viscosity of 0.45 to 1.0 dl / g.
5% by weight and a compound having three or more carboxyl groups and / or hydroxyl groups in the molecule contain 0.02 to
Polyester resin characterized by being blended with 5 to 80% by weight of a branched copolymerized polyethylene terephthalate resin (B) having an intrinsic viscosity of 0.6 dl / g or more copolymerized by 8 mol% and extruded. Manufacturing method of decorative sheet. 9. One of the polyethylene terephthalate-based resin (A) and the branched copolymerized polyethylene terephthalate-based resin (B) is charged from a raw material inlet of an extruder, and after melting, the other component is added. The method for producing a decorative sheet made of a polyester resin according to claim 8, wherein the extruder is added in the middle of the extruder and extruded. 10. A container formed by thermoforming the polyester resin decorative sheet according to claim 1.