JP2008007605A - Polyester resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin sheet which scarcely causes wrinkles, cracks nor lifting when applied, generates no plate-out when in calendering, and has excellent surface status. <P>SOLUTION: The polyester resin sheet is obtained by molding a resin composition comprising a polyester resin (a) obtained by reacting 80-100 mol% of at least one member selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and isophthalic acid with 80-100 mol% of a diol having a carbon number of 2-10, a polyester resin (b) obtained by reacting 50-95 mol% of terephthalic acid and 5-50 mol% of isophthalic acid or its ester-formed derivative with a diol including ethylene glycol and a polyether having a repeating unit having a carbon number of not less than 2, a lubricant (c), and at least two plate-out preventing agents (d) wherein the blended ratio of the polyester resin (a) to the polyester resin (b) [(a)/(b)] is 2/98-45/55 on the basis of mass. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a polyester resin sheet.

A decorative sheet is used as a surface decoration material for building materials, furniture, cabinets for home appliances, and the like. Such decorative sheets are used by sticking to woody materials such as wood, plywood, laminated wood, particle board, hardboard, etc., vacuum press molding, pressure press molding, membrane press molding, wrapping. It is used by pasting together by processing.

Conventionally, as such a decorative sheet, a vinyl chloride resin (PVC) sheet in which an opaque vinyl chloride resin film provided with a printing ink layer as a base sheet and a transparent vinyl chloride resin film as a protective sheet is laminated has been used. Has been. Such a vinyl chloride resin decorative sheet is most used as a decorative sheet having a high degree of freedom, such as the colorability, embossability, and printability of the vinyl chloride resin.

However, the above-mentioned decorative sheet made of vinyl chloride resin has the problem of dioxin, the problem that hydrogen chloride gas is generated at the time of combustion, etc., so the development of a decorative sheet using a non-vinyl chloride resin material is desired. . For this reason, for example, polyester resins such as polyethylene terephthalate have attracted attention as non-vinyl chloride resin materials, and sheets using such polyester resins are disclosed in Patent Documents 1-2.

Patent Document 3 includes terephthalic acid / ethylene glycol / polytetramethylene glycol / 1,4-cyclohexanedimethanol copolymer, terephthalic acid / ethylene glycol / polytetramethylene glycol / 1,4-cyclohexanedimethanol copolymer, And the composition for flexible polyester decorative sheets which consists of wax is disclosed. Patent Document 4 discloses a resin sheet obtained by molding a composition containing a completely amorphous polyester resin, a thermoplastic polyester elastomer, and a lubricant.

However, these sheets are higher in rigidity than soft PVC, are easily wrinkled and cracked during processing and construction, and are inferior in bending workability and stretch workability. Furthermore, there is a disadvantage that the decorative sheet is likely to float during construction.
Furthermore, when these films are produced by calendering, plate-out is likely to occur, and films having uneven surfaces and gloss unevenness are often formed.
Accordingly, it has been desired to develop a film that is easy to produce, similar to a decorative sheet made of soft PVC, is excellent in workability and workability, has a good surface condition, and is excellent in texture.

Japanese Patent Laid-Open No. 9-300564 JP 2000-290415 A JP 2003-246916 A Japanese Patent Laid-Open No. 2004-91795

The present invention provides a polyester resin sheet that has a good surface condition, has a good texture, is not easily wrinkled or cracked during construction, does not easily float, and does not generate plate-out in calendering. For the purpose.

The present invention includes a dicarboxylic acid component containing 80 to 100 mol% of at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid, and a carbon number of 2 to 10 Polyester resin (a) comprising as a constituent component a diol component containing 80 to 100 mol% of a diol, terephthalic acid 50 to 95 mol%, and a dicarboxylic acid component containing 5 to 50 mol% of isophthalic acid or an ester-forming derivative thereof A polyester resin (b), a lubricant (c), and two or more kinds of plate-out agents (d), which comprise a diol component containing ethylene glycol and a polyether having a repeating unit having 2 or more carbon atoms The mixing ratio of the polyester resin (a) and the polyester resin (b) [(a) / (b) Is a polyester resin sheet, characterized in that it is obtained by molding a resin composition which is 2 / 98-45 / 55 by weight.

The plate-out inhibitor (d) is preferably silica and an acrylic oligomer.
The blending ratio of the silica and the acrylic oligomer is preferably 1/1 to 10/1 in terms of solid content.
The total content of the plate-out inhibitor (d) is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total resin solid content of the polyester resin (a) and the polyester resin (b). Preferably there is.
It is preferable that content of the said polyether is 0.1-40 mass% in 100 mass% of resin solid content of a polyester resin (b).
The resin composition preferably contains a colorant.
It is preferable to be obtained by the above calendar processing.
Hereinafter, the present invention will be described in detail.

The polyester resin sheet of the present invention comprises a dicarboxylic acid component containing at least one selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid, and carbon. Polyester resin (a) comprising as a constituent component a diol component containing 80 to 100 mol% of a diol of 2 to 10 mol, 50 to 95 mol% of terephthalic acid, and 5 to 50 mol% of isophthalic acid or an ester-forming derivative thereof A polyester resin (b), a lubricant (c), and two or more kinds of plate-outs comprising a dicarboxylic acid component containing, a diol component containing ethylene glycol, and a polyether having a repeating unit having 2 or more carbon atoms It is obtained by molding a resin composition containing the inhibitor (d). In this invention, a synergistic effect arises by using the resin composition which mix | blended specific amount of said specific component, As a result, the effect described below is exhibited.

Since the polyester resin sheet of the present invention is obtained by molding the resin composition, when the polyester resin sheet is applied to a surface having a cubic curved surface, the sheet can be satisfactorily stretched on the curved surface. it can. For this reason, it can prevent that a wrinkle arises at the time of construction and an appearance is impaired.

Since the said polyester resin sheet is obtained by shape | molding the said resin composition, the waist of a sheet | seat is also favorable. For this reason, when the polyester resin sheet is a sheet having a printed pattern, even if the sheet is applied to a cubic curved surface, the elongation becomes too large, and the printed pattern is stretched or the concealability is lowered. Can be prevented. Moreover, since the said polyester resin sheet is a thing excellent in the softness | flexibility, when the said polyester resin sheet is constructed | assembled to a tertiary curved surface, it can prevent that troubles, such as a dregs and peeling, generate | occur | produce after construction.

Since the polyester resin sheet is obtained by molding the resin composition, when the polyester resin sheet is a sheet having a printed pattern, the polyester resin sheet has excellent adhesion of the colored ink used for printing. is there. Therefore, when an adhesive tape is affixed on the polyester resin sheet having a printed pattern and then peeled off, the colored ink can be prevented from being peeled off together with the adhesive tape.

Since the said resin composition contains the specific component mentioned above, it has the outstanding calendar workability. For this reason, the said polyester resin sheet can be easily obtained by calendering. For example, when a sheet is formed by calendering, it is possible to prevent adhesion to the calender roll, and therefore, it is possible to prevent the occurrence of problems such as the inability to peel off the sheet from the roll. Moreover, since it is possible to prevent the occurrence of plate-out in calendering, a sheet having a good surface condition and excellent texture can be obtained.

The polyester resin (a) includes a dicarboxylic acid component containing 80 to 100 mol% of at least one selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid, and carbon. A diol component containing 80 to 100 mol% of a diol having a number of 2 to 10 is used as a constituent component. Thereby, it is possible to obtain excellent formability to a cubic surface, ink adhesion, adhesion suitability, and calendar workability.

In the dicarboxylic acid component, the naphthalene dicarboxylic acid may be any isomer of various isomers or a mixture of isomers, among which 1,4-, 1,5-2, The 6,6- and 2,7-isomers are preferred. It is also possible to use cis, trans or cis / trans isomer mixtures of 1,4-cyclohexanedicarboxylic acid. Sulfoisophthalic acid can also be used.

The dicarboxylic acid component contains 80 to 100 mol% of at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid. If it is less than 80 mol%, moldability to a cubic surface, ink adhesion, adhesiveness, and calendar workability may be reduced. The amount is the total amount of the components.

The dicarboxylic acid component may contain other dicarboxylic acids having 4 to 40 carbon atoms. Examples of the other dicarboxylic acids include succinic acid, glutaric acid, azelaic acid, adipic acid, suberic acid, sebacic acid, and dimer acid. Content of the said other dicarboxylic acid is 20 mol% or less in 100 mol% of said dicarboxylic acid components. The dicarboxylic acid in the dicarboxylic acid component may be used alone or in combination of two or more.

The diol component contains a diol having 2 to 10 carbon atoms.
The diol having 2 to 10 carbon atoms is not particularly limited, and conventionally known diols can be used. Among them, ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol and a mixture thereof. Is preferable in that the effect of the present invention can be obtained.

The diol component contains 80 to 100 mol% of a diol having 2 to 10 carbon atoms.
If it is less than 80 mol%, moldability to a cubic surface, ink adhesion, adhesiveness, and calendar workability may be reduced. The amount is the total amount of diols having 2 to 10 carbon atoms contained in the diol component.

It is particularly preferable that the diol component contains 10 to 100 mol% of 1,4-cyclohexanedimethanol and 90 to 0 mol% of ethylene glycol in order to obtain the effects of the present invention.

Examples of the diol having 2 to 10 carbon atoms include, in addition to those described above, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8 -Octanediol, 2,2,4-trimethyl-1,3-pentanediol, propylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like. The diol in the diol component may be used alone or in combination of two or more.

The polyester resin (a) can be produced by a conventionally known method.
The polyester resin (a) may contain a stabilizer in addition to the above components. Thereby, oxidative decomposition during processing on the roll can be prevented.

Examples of the stabilizer include esters such as distearyl thiodipropionate or dilauryl thiodipropionate; phenolic stabilizers such as butylated hydroxytoluene; and phosphorus-containing stabilizers. Examples of commercially available products include Irganox 1010, Irgafoss (manufactured by Ciba Geigy), Etanox 330 (manufactured by Ethyl), Weston (manufactured by GE Specialty Chemicals), and the like.

The polyester resin (a) is composed of trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, and 3-hydroxyglutaric acid. And the like.

The polyester resin (a) may contain conventional known additives in addition to the above components. Examples of the additive include a plasticizer, a dye, a colorant, a pigment, a filler, a matting agent, an anti-tacking agent, an antistatic agent, glass, an impact resistance improving agent, and a flame retardant.

In the said polyester resin (a), it is preferable that content of the said stabilizer and additive is 0.01-10 mass% in 100 mass% (solid content) of the said polyester resin composition. The content can be appropriately determined in consideration of the apparatus, material, method conditions, and sheet thickness.

As a commercial item of the said polyester resin (a), TSUNAMI GS-2, PETG 6863 (made by Eastman Chemical Co., Ltd.), Sky Green K2012 (made by SK Chemical Co., Ltd.) can be mentioned, for example.

The polyester resin (b) comprises 50 to 95 mol% terephthalic acid and a dicarboxylic acid component containing 5 to 50 mol% isophthalic acid or an ester-forming derivative thereof, a diol component containing ethylene glycol, and 2 or more carbon atoms. A polyether having a repeating unit is a constituent component.

In the polyester resin (b), the dicarboxylic acid component contains terephthalic acid and isophthalic acid or an ester-forming derivative thereof.
In the polyester resin (b), the dicarboxylic acid component contains 50 to 95 mol% of terephthalic acid in 100 mol% of the dicarboxylic acid component. Thereby, the effect of the present invention can be obtained more effectively. If it is less than 50 mol%, it is difficult to proceed the polymerization to a predetermined degree of polymerization, and there is a possibility that a moldable resin cannot be obtained. If it exceeds 95 mol%, the transparency and flexibility of the polyester resin (b) may be lowered.

In the polyester resin (b), the dicarboxylic acid component contains 5 to 50 mol% of isophthalic acid or an ester-forming derivative thereof in 100 mol% of the dicarboxylic acid component. If it is less than 5 mol%, the transparency and flexibility of the polyester resin (b) may be lowered. When it exceeds 50 mol%, it becomes difficult to proceed the polymerization to a predetermined polymerization degree, and there is a possibility that a moldable resin cannot be obtained.

In the zirconic acid component in the polyester resin (b), the terephthalic acid and the isophthalic acid or an ester-forming derivative thereof are preferably contained in 80 to 100 mol% in 100 mol% of the dicarboxylic acid component, 90 More preferably, it is contained in an amount of ˜100 mol%. If it is less than 80 mol%, the mechanical properties of the polyester resin (b) may be lowered. In addition, the content of the terephthalic acid and the isophthalic acid or the ester-forming derivative thereof is a total amount thereof.

In the polyester resin (b), the dicarboxylic acid component may contain an aliphatic dicarboxylic acid such as adipic acid or sebacic acid as long as the effects of the present invention are not impaired. The content of the aliphatic dicarboxylic acid is preferably 20 mol% or less in 100 mol% of the carboxylic acid component.

In the polyester resin (b), the diol component contains ethylene glycol.
The ethylene glycol content is preferably 50 to 100 mol% in 100 mol% of the diol component. If it is less than 50%, the reactivity at the time of polymerization may decrease, and it may be difficult to obtain a resin having a predetermined polymerization degree. More preferably, it is 60-100 mol%, and it is still more preferable that it is 70-100 mol%.

In the polyester resin (b), the diol component contains other diols such as neopentyl glycol, cyclohexane dimethanol, bisphenol compound or an ethylene oxide adduct thereof as long as the effects of the present invention are not impaired. It may be.

Examples of the ethylene oxide adduct of the bisphenol compound or derivative thereof include those having structures represented by the following formulas (1) and (2).

(In the formula, X represents CH ₂ , C (CH ₃ ) ₂ , O or SO _2, and n and m represent integers satisfying 2 ≦ n + m ≦ 6.)

(In the formula, X represents CH ₂ , C (CH ₃ ) ₂ , O or SO ₂ , R represents a C _{1 to} C ₅ alkyl group or halogen group, and n and m satisfy 2 ≦ n + m ≦ 6. Integers a and b represent integers of 1 to 4.)
Especially, the bisphenol A ethylene oxide adduct which has a structure represented by following formula (3) is especially preferable.

(In the formula, n and m are integers satisfying 2 ≦ n + m ≦ 6.)
The polyester resin (b) contains a polyether having a repeating unit having 2 or more carbon atoms as a constituent component. It is preferable that content of the said polyether is 0.1-40 mass% in 100 mass% of resin components which comprise the said polyester resin (b). There exists a possibility that the softness | flexibility of the obtained polyester resin (b) may not be enough that it is less than 0.1 mass%. When it exceeds 40 mass%, there exists a possibility that calendar workability may fall. More preferably, it is 0.5-35 mass%, More preferably, it is the range of 0.5-25 mass%.

The polyether is not particularly limited, and examples thereof include polyethylene glycol and polyoxytetramethylene glycol.
The polyethylene glycol preferably has a number average molecular weight of 300 to 20,000. The polyoxytetramethylene glycol preferably has a number average molecular weight of 300 to 4000. If it is less than the lower limit, the effect of imparting flexibility is small, and if it exceeds the upper limit, the compatibility with the resin is lowered and the transparency may be impaired. Of these, polytetraoxymethylene glycol is preferable in terms of weather resistance and the like.

The polyester resin (b) is particularly preferably a polyester resin containing terephthalic acid, isophthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol and polyoxytetramethylene glycol as constituent components. When such a polyester resin is used, the effect of the present invention can be obtained more effectively.

The polyester resin (b) may contain additives such as stabilizers in order to improve the thermal stability and weather resistance of the resin. Examples of the additive include phenolic antioxidants, thioether antioxidants, and phosphite stabilizers. As a method for producing the polyester resin (b), a known direct polymerization method or transesterification method can be used, and the degree of polymerization is not particularly limited, but intrinsic viscosity (equal mass mixing of phenol and tetrachloroethane) Those having a measured value at 25 ° C. in the solution of 0.5 or more are preferred.

As a commercial item of the said polyester resin (b), Dianite DN-149 (made by Mitsubishi Rayon Co., Ltd.) can be mentioned, for example.

In the resin composition, the mixing ratio [(a) / (b)] of the polyester resin (a) and the polyester resin (b) is 2/98 to 45/55 on a mass basis. When the mixing ratio of the polyester resin (a) is less than 2% by mass, the film / sheet is too soft and has low stiffness, and when it is applied to a surface having a tertiary curved surface, wrinkles are likely to occur and the appearance may be impaired. There is. When the mixing ratio of the polyester resin (a) exceeds 45%, the sheet becomes hard, and when it is applied to a surface having a tertiary curved surface or the like, the elongation is small, and there is a possibility that problems such as cracking and peeling will occur after the application. is there. The mixing ratio is preferably 30/70 to 45/55.

The resin composition contains a lubricant (c). When calendering is performed using the composition having the above mixing ratio, the metal slipperiness is poor and it is difficult to peel off the film / sheet from the calender roll. However, by adding the lubricant (c), the workability is improved. Can be improved.

The lubricant (c) is not particularly limited, and conventionally known lubricants can be used, but fatty acid waxes such as stearic acid and oleic acid; hydrocarbon waxes such as paraffin, polyethylene and polypropylene; aliphatic metals A wax-based lubricant such as a soap-based or aliphatic ester-based wax; an aliphatic amide-based wax is preferable. These composite waxes may be used. Among these, it is more preferable to use an ester-based or polyethylene-based wax composite from the viewpoint of obtaining the effects of the present invention. Here, the ester wax is preferably a montanic acid wax, and the polyethylene wax preferably has a low molecular weight. These lubricants (c) may be used independently and may use 2 or more types together.

It is preferable that content of the said lubricant (c) is 0.5-5.0 mass parts with respect to 100 mass parts of total resin solid content of the said polyester resin (a) and the said polyester resin (b). If it is out of the above range, calendar workability may be reduced. The content is more preferably 0.5 to 3.0 parts by mass.

The said resin composition contains 2 or more types of plate-out prevention agents (d).
When the resin composition containing a polyester resin used to form a sheet is calendered by adding a function-imparting additive depending on the lubricant or application, these additives and the polyester-based resin cause thermal degradation, A plate-out occurs on the calender roll or an embossing roll which is a subsequent process, and the surface state of the formed film is not smooth or glossy. If it does so, printability and design nature may be spoiled in the later processing of a film.
In the present invention, by adding two or more kinds of plate-out inhibitors, when molding by calendering, plate-out can be prevented during processing, and a sheet having a good surface state can be obtained.

Examples of the plate-out agent (d) include alkylphenol phosphates, ricinoleic acid, acrylic oligomers, polybutene organic substances, organic metals, inorganic oxides such as silica, etc., among which acrylic oligomers And silica are preferred. By using these together, it is possible to suitably prevent plate-out when molded by calendering and obtain a resin sheet having a good surface state.
By adding the above-mentioned silica, it is presumed that the heat-degraded product of the polyester resin or the ejected product of the additive is absorbed by the porous silica pores, or the ejected product adhering to the roll surface is scraped off by the silica. The Moreover, it is guessed that the said acrylic oligomer forms a thin film | membrane on the film containing a heat deterioration thing and an additive. Therefore, it is speculated that these two synergistic effects can suitably suppress plate-out in calendering and obtain a polyester resin sheet having a good surface condition.

Silica treated with coupling agents such as silane, titanate, aluminate and zircoaluminum, surfactants such as phosphoric acid and fatty acid, and surface treatment agents such as oils and fats It may be.

The primary average particle diameter of the silica is preferably 10 to 10,000 nm. If it is less than 10 nm, it may be difficult to obtain. If it exceeds 10,000 nm, the effects of the present invention may not be obtained. The value of the primary average particle diameter is a value obtained by a conventionally known measurement method.

Examples of commercially available silica products include “Fine Seal B” (trade name, manufactured by Tokuyama), “Fine Seal” (trade name, manufactured by Tokuyama), and “Silicia” (trade name, manufactured by Fuji Silysia Chemical). be able to. These may be used alone or in combination of two or more.

Examples of acrylic oligomers include urethane acrylate oligomers, ester acrylate oligomers, epoxy acrylate oligomers, and acrylic resin acrylates.
Examples of the urethane acrylate oligomer include those obtained by chemically bonding a high molecular weight isocyanate and an acrylate having a hydroxyl group.
The acrylic resin acrylate is a copolymer of (meth) acrylate monomers having a functional group such as a carboxyl group, an epoxy group, and a hydroxyl group in advance in an acrylic copolymer resin mainly composed of polymethyl methacrylate. Examples include those in which a double bond is introduced by addition reaction with a (meth) acrylate monomer having a functional group that undergoes an addition reaction corresponding to the functional group.
The weight average molecular weight of the acrylic oligomer is usually 2000 to 12000.

Examples of commercially available acrylic oligomers include “LS-5” (trade name, manufactured by Katsuta Chemical Industries).
These may be used alone or in combination of two or more.

The mixing ratio of the silica and the acrylic oligomer is preferably 1/1 to 10/1 in terms of solid mass. If it is less than 1/1, there is a risk of silica plate-out. If it exceeds 10/1, the slipperiness on the calendar roll may be reduced. The blending ratio is more preferably 2/1 to 10/1.

The total content of the plate-out inhibitor (d) is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total resin solid content of the polyester resin (a) and the polyester resin (b). It is preferable. If it is less than 0.1 parts by mass, there is a possibility that plate-out by the lubricant (c) or other additives cannot be prevented. If it exceeds 3.0 parts by mass, the plate-out preventing agent may plate out. The content is more preferably 0.5 to 2.0 parts by mass.

The resin composition may also contain an antibacterial and antifungal agent. The antibacterial and antifungal agent is not particularly limited, and examples thereof include organic types such as imidazole type and inorganic types such as inorganic silver.

The resin composition may also contain an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and examples of the ultraviolet absorber include benzophenone, salicylate, benzotriazole, and cyanoacrylate.

The resin composition may contain a colorant.
As the colorant, conventionally known dyes and pigments used for coloring sheets can be used. For the coloring of the polyester resin sheet, a transparent colored sheet can be obtained by molding a resin composition to which a colorant is added.
The said resin composition may contain the other additive used for a resin sheet.

The polyester resin sheet preferably has a thickness of 0.05 to 0.3 mm. If it is less than 0.05 mm or more than 0.3 mm, the film formation and surface smoothness may be lacking, and calendar workability may be difficult. The thickness is more preferably 0.05 to 0.2 mm.

The polyester resin sheet has a 5% modulus in a tensile test based on JIS K6732, and a range of 5 to 35 MPa in both the flow direction and the width direction under the conditions of a measurement atmosphere temperature of 23 ± 2 ° C. and a tensile speed of 200 mm / min. Is preferred. If it is within the above range, excellent formability to a cubic surface, ink adhesion when printed, adhesive strength when pasted to a substrate, adhesive properties such as adhesive residue when peeled, and calendar Workability can be obtained effectively. If it is less than 5 MPa, the film may be stretched during printing and pattern misalignment may occur, or wrinkles may occur during construction on a tertiary curved base material, and pattern elongation may occur. If it exceeds 35 MPa, the film becomes hard, and there is a possibility that the alignment along the third-order curved surface substrate will be deteriorated. In addition, the film may float over time after being attached.

The measurement conditions for the 5% modulus are: sample size: 19 mm width strip, chuck interval: 50 mm, mark interval: 25 mm, and tensile speed: 50 mm / min.
The above-mentioned polyester resin sheet having 5% modulus is selected from, for example, the above-described polyester resin (a), polyester resin (b), lubricant (c), and two or more kinds of plate-out preventing agents (d). Can be obtained.

The said polyester resin sheet can be manufactured by a conventionally well-known method, for example, can be manufactured by extrusion, a calendar process, etc. Especially, since the polyester resin sheet of this invention is obtained using the said resin composition, it is preferable that it is what is obtained by calendering. When calendar processing is used, it is possible to prevent problems such as not being peeled off from the calendar roll.

When the polyester resin sheet is obtained by calendering, the resin composition preferably has a melt flow rate (230 ° C., 37.3 N) of 15 or less. Thereby, the viscosity of the resin composition in the molten state within the range of 150 to 200 ° C. can have good kneading efficiency and good rotation of the bank. For this reason, a uniform thin film can be obtained by calendering the resin composition.

As for the said resin composition, it is more preferable that a melt flow rate (230 degreeC, 37.3N) exists in the range of 1-15. By setting the melt flow rate to 1 or more, when calendering using calendering equipment for polyvinyl chloride resin, it is possible to prevent deterioration of calenderability due to the viscosity of the resin composition being too high. it can. The calendar format used for the calendar processing is not particularly limited, and examples thereof include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.

The polyester resin sheet may be a laminated sheet. That is, in this case, the laminated sheet is obtained by laminating a base material layer and a surface protective layer, and both the base material layer and the surface protective layer are made of the above-described polyester resin sheet. By using the above-described polyester resin sheet for both layers, excellent formability to a cubic surface, ink adhesion when printed, adhesion suitability, and calendar workability can be effectively obtained.

In the laminated sheet, either or both of the base material layer and the surface protective layer may be colored sheets. In this case, the colored sheet can be obtained by molding a resin composition containing the colorant described above.

The base material layer preferably has a thickness of 0.05 to 0.3 mm. When the thickness is less than 0.05 mm or more than 0.3 mm, the film formation and the surface smoothness are lacking and the calendar workability is difficult. More preferably, it is 0.07 to 0.2 mm.
The surface protective layer preferably has a thickness of 0.04 to 0.2 mm.

The laminated sheet may have a printed layer. In this case, examples of the laminated sheet include those obtained by laminating a base material layer, a printing layer, and a surface protective layer in this order. The laminated sheet having the printing layer is excellent in the adhesion of the colored ink used for printing. Such an effect is an effect acquired by using the polyester resin sheet obtained by shape | molding the resin composition mentioned above.

The printed layer can be formed on the substrate layer or the surface protective layer by a known printing method such as a gravure printing method, a flexographic printing method, a silk screen printing method, for example, on the substrate layer or the surface. A metallic print pattern can be formed on the protective layer by printing an arbitrary pattern such as wood grain or using an ink prepared by mixing an aluminum paste.

The laminated sheet may have a pressure-sensitive adhesive layer.
When the laminated sheet has a pressure-sensitive adhesive layer, the polyester resin sheet to be used is obtained by molding the resin composition. Therefore, when the laminated sheet is attached, a large adhesive force can be obtained. it can. In addition, when the attached laminated sheet is peeled off, it is possible to prevent the adhesive from remaining on the attached base material (adhesive residue).

The pressure-sensitive adhesive layer can be formed by a conventionally known pressure-sensitive adhesive, and can be formed by using, for example, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive.
The acrylic pressure-sensitive adhesive is composed of an acrylic polymer, and examples of the acrylic polymer include a homopolymer of (meth) acrylic acid alkyl ester or a copolymer thereof. it can. As alkyl in the said (meth) acrylic-acid alkylester, C4-C12 linear or branched alkyl is preferable.

Examples of the rubber adhesive include polyisobutylene / polybutene, styrene / diene / styrene block copolymer, styrene / butadiene, nitrile, chloroprene, vinylpyridine, polyisobutylene, butyl, isoprene, A rubber-based pressure-sensitive adhesive made of isobutylene or the like can be mentioned. Of these, polyisobutylene, styrene / diene / styrene block copolymer (for example, styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene / styrene block copolymer (SIS), etc.) and the like are preferable.

The laminated sheet may have a release layer. The release layer protects the pressure-sensitive adhesive layer until the pressure-sensitive adhesive sheet is attached, and is peeled off at the time of attachment. In this case, examples of the laminated sheet include those obtained by laminating a base material layer, a printing layer, a surface protective layer, a pressure-sensitive adhesive layer, and a release layer in this order.

Examples of the release layer include high-density base paper such as glassine paper, clay-coated paper, craft paper, or high-quality paper, casein, dextrin, starch, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, styrene- Eyes mainly composed of natural or synthetic resins and pigments such as butadiene copolymer, methyl methacrylate-butadiene copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, acrylate ester copolymer Sheet provided with a stop layer; Laminated paper obtained by laminating polyethylene or the like on kraft paper or high-quality paper; Dry weight of water, solvent-type or useless type silicone resin or fluororesin on a sheet of polypropylene or the like in normal 0.05~3g / ^{m 2} coating Then, what formed the mold release layer by thermosetting, electron radiation curing, etc. can be used. Especially, the polypropylene etc. which were processed with the silicone resin can be used suitably from an environmental viewpoint.

The laminated sheet can be obtained by a conventionally known method. That is, the base material layer and the surface protective layer obtained by the above-described calendering or the like can be prepared using a conventionally known laminating method. Especially, since the preparation method is simple and the cost is low, it is preferable that the base material layer and the surface protective layer are prepared by a method of attaching by heat lamination.

The laminated sheet may be embossed.
The polyester resin sheet and the laminated sheet can be suitably used as a decorative sheet.

When the laminated sheet has an adhesive layer, the laminated sheet preferably has an adhesive strength measured according to JIS Z0237 of 10 N / 25 mm or more. The adhesive strength is as follows: a sheet of width 25 mm × length 150 mm is attached to an aluminum plate (JIS A5052), left at a temperature of 23 ° C. for 24 hours, and peeled off at a pulling speed of 300 mm / min and a pulling angle of 180 degrees. It is adhesive force (N / 25mm) at the time. Similarly, the adhesive strength after standing at a temperature of 60 ° C. for 7 days is preferably 10 N / 25 mm or more. In this case, the laminated sheet has excellent adhesion suitability.

Hereinafter, the example of the said lamination sheet is demonstrated using figures.
FIG. 1 is a schematic view of a laminated sheet in which a surface protective layer 1, a printing layer 2, a base material layer 3, an adhesive layer 4 and a release layer 5 are laminated in this order. The laminated sheet is obtained, for example, by molding the resin composition described above with the surface protective layer 1 and the base material layer 3, and thus has excellent moldability to a cubic surface when printed. It has ink adhesion, adhesion suitability, and calendar processability. Moreover, the surface protective layer 1 and the base material layer 3 can be favorably manufactured by calendering.

The laminated sheet can be produced by attaching the base material layer and the surface protective layer by thermal lamination. Thereby, a base material layer and a surface protective layer can fully be affixed, and it can manufacture very simply.

The polyester resin sheet of the present invention is a resin composition comprising the polyester resin (a) and the polyester resin (b) mixed at a specific blending ratio, and further containing the lubricant (c) and the plate-out inhibitor (d). It is obtained by molding. For this reason, it has excellent moldability to a cubic surface, ink adhesion when printed, and calendar workability. Moreover, it is also excellent in texture. Therefore, the polyester resin sheet and the laminated sheet can be suitably used as a decorative sheet.

Since the polyester resin sheet of the present invention has the above-described configuration, it has excellent moldability to a cubic surface, ink adhesion when printed, and calendar workability.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

Examples 1-4 and Comparative Examples 1-4
The following materials were blended as shown in Table 1 to produce a 0.08 mm film using a 10-inch inverted L-type calendar. In addition, the temperature of a calender roll is 175 degreeC and the temperature of an embossing roll is 40 degreeC.
(1) Polyester resin 1 (“TSUNAMI GS-2” manufactured by Eastman Chemical Co.)
(2) Polyester resin 2 (“Dianite DN-149” manufactured by Mitsubishi Rayon Co., Ltd., terephthalic acid / isophthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol / polyoxytetramethylene glycol, MFR 24 g / 10 min (23 ° C./2 .16 kg))
(3) Lubricant (Daikyo Kasei Kogyo "RX-PO-11 [Ester (montanic acid), polyethylene (low molecular weight) wax composite]")
(4) Plateout prevention agent a: “Fine Seal B” manufactured by Tokuyama Corporation, ultrafine powder wet silica (5) Plateout Prevention Agent b: “Fine Seal X-80” manufactured by Tokuyama Corporation, ultrafine powder wet silica (6) Plate Out prevention agent c: “LS-5” manufactured by Katsuta Chemical Industries, Ltd., acrylic oligomer

[Evaluation]
(Calendar workability)
About the film (sheet) obtained above, calendar workability was evaluated according to the following criteria. The results are shown in Table 1.
Plate-out (1): A case where the plate-out to the calendar roll did not occur, and a case where the plate-out occurred.
Plate-out (2): ○ when the plate-out of the embossing roll did not occur, and × when it occurred.

(Formability to a cubic surface)
After performing adhesive processing by applying an adhesive to the back of the film, it was evaluated by the following method. The results are shown in Table 1.
(1) Substrate used: MDF (height 50 mm, vertical and horizontal 200 mm each, corner 10R)
(2) Construction method: While heating the film with a dryer, the squeegee is pressed and bonded to the MDF. (Stop the film edge of the part wrapped around the back of the MDF with seal tape)
(3) Determination method (circle); The film was appropriately shape | molded along the base-material shape, and it was able to be affixed without impairing an external appearance (design).
X: The elongation at the R portion was insufficient, wrinkled, or because the film was weak, the elongation increased, the printed pattern was elongated, and the concealability was low.

(Ink adhesion)
A film printed with a wood grain pattern with a colored ink mainly composed of a two-component curable urethane resin is left in a gear oven at 60 ° C. for 7 days, and then a commercially available adhesive tape is applied to the obtained film. And then evaluated by peeling.
○: Ink remained completely on the film side.
X: The ink was taken on the adhesive tape.

From Table 1, the film obtained by the Example did not generate | occur | produce a plate-out and was able to form a favorable film. On the other hand, what was obtained by the comparative example generate | occur | produced plate-out and was not able to form a favorable film.

The polyester resin sheet of the present invention can be suitably used as a decorative sheet.

It is an example of the schematic diagram of the lamination sheet which used the polyester resin sheet of this invention as a surface protective layer and a base material layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface protective layer 2 Printing layer 3 Base material layer 4 Adhesive layer 5 Release layer

Claims (7)

A dicarboxylic acid component containing 80 to 100 mol% of at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid, and 80 diols having 2 to 10 carbon atoms A polyester resin (a) containing as a constituent component a diol component containing ˜100 mol%,
A dicarboxylic acid component containing 50 to 95 mol% terephthalic acid and 5 to 50 mol% isophthalic acid or an ester-forming derivative thereof, a diol component containing ethylene glycol, and a polyether having a repeating unit having 2 or more carbon atoms Polyester resin (b) as a constituent,
Containing a lubricant (c), and two or more plate-out preventing agents (d),
The mixing ratio [(a) / (b)] of the polyester resin (a) and the polyester resin (b) is obtained by molding a resin composition that is 2/98 to 45/55 on a mass basis. Polyester resin sheet characterized by The polyester resin sheet according to claim 1, wherein the plate-out inhibitor (d) is silica and an acrylic oligomer. The polyester sheet according to claim 2, wherein the mixing ratio of silica and acrylic oligomer is 1/1 to 10/1 in terms of solid content. The total content of the plate-out inhibitor (d) is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total resin solid content of the polyester resin (a) and the polyester resin (b). 2 or 3 polyester resin sheet. The polyester resin sheet according to claim 1, 2, 3 or 4, wherein the content of the polyether is 0.1 to 40% by mass in 100% by mass of the resin solid content of the polyester resin (b). The polyester resin sheet according to claim 1, 2, 3, 4 or 5, wherein the resin composition contains a colorant. The polyester resin sheet according to claim 1, which is obtained by calendering.

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