JP2007210270A - Laminated polyester sheet and decorating sheet using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated polyester sheet and a decorating sheet superior in use for a building material and an interior. <P>SOLUTION: The laminated polyester sheet has two constructing layers of at least A/B, the A layer is a protection sheet layer and the B layer is an adhesive layer, and also satisfies conditions of (1) and (2) as below. (1) The A layer consists of a polyester having a glass transition temperature TgA in a range of 40 to 70°C and further has a crystalline parameter ΔTcg in a range of 30 to 60°C. (2) The B layer consists of a polyester having a glass transition temperature TgB in a range of -20 to 20°C and further has a melting temperature TmB in a range of 120 to 210°C. The decorating sheet keeps the laminated polyester sheet overlying an interior substrate so that the A layer of the laminated polyester sheet makes an outer surface. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative sheet having design properties, and in particular, uses such as industrial materials and packaging materials that require scratch resistance, transparency, moldability, heat resistance, chemical resistance, and thermal adhesiveness. More specifically, the present invention relates to a sheet for building materials and interior that is excellent in embossability, stain resistance, and chemical resistance.

  As a sheet conventionally used for building materials and interiors, a polyvinyl chloride film is typical. This polyvinyl chloride film is preferably used because it has excellent weather resistance and is suitable not only for various processes such as embossing but also at a low cost.

  However, polyvinyl chloride film has problems such as generation of toxic gas when the film burns due to fire, etc., and bleed-out of plasticizer. Therefore, due to recent environmental needs, new building materials and interior use There is a need for films. Scratch resistance, contamination resistance, chemical resistance, and embossability are required as characteristics required for building materials and interior films.

  As an alternative to the polyvinyl chloride film, a configuration using a polyolefin film or a polyester film has been proposed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, although the polyolefin-based film has good contamination resistance and chemical resistance, the embossability is insufficient. Polyester film has excellent scratch resistance, stain resistance, chemical resistance, and embossability, but an adhesive must be used for bonding to the base material, and there is a film with excellent thermal adhesiveness. It was desired.

  As an improvement in thermal adhesiveness, a composite film for interior materials has been proposed in which a polybutylene terephthalate-based polyester resin layer having a melting point of 150 to 215 ° C. is provided (for example, see Patent Document 4). However, since the surface layer film is a biaxially stretched film, it has excellent scratch resistance, stain resistance, chemical resistance, heat resistance, and thermal adhesiveness, but has poor formability such as embossability. Moreover, the copolymer polyester was used and it was not the film which considered cost.

On the other hand, a laminated film in which a highly crystalline polyester is laminated on one side of a flexible polyester has been proposed (see, for example, Patent Document 5). Such laminated films are mainly intended to suppress changes over time in flexibility and transparency, and there is no description or suggestion of film formability or chemical resistance improvement, scratch resistance, contamination resistance, chemical resistance, embossability At present, building materials and interior sheets that satisfy all the required properties such as thermal adhesiveness have not been achieved.
JP 2000-094609 A Japanese National Patent Publication No. 2002-092689 Japanese Patent Application Laid-Open No. 2002-219776 JP-A-10-278208 Japanese Patent Laid-Open No. 05-131601

  In view of the background of the prior art, the present invention satisfies the basic required characteristics of a building material sheet and interior sheet such as scratch resistance, chemical resistance, embossability, and thermal adhesiveness, in addition to heat resistance and aging resistance. It is an object of the present invention to provide a laminated polyester sheet and a decorative sheet excellent in whitening property.

The present invention employs the following means in order to solve such problems. That is, the laminated polyester sheet of the present invention is a laminated polyester sheet having at least a two-layer structure of A / B, wherein the A layer is a protective sheet layer, the B layer is an adhesive layer, and the following (1) (2) is satisfied.
(1) The protective sheet layer of layer A is a polyester having a glass transition temperature TgA in the range of 40 to 70 ° C and a crystallinity parameter ΔTcg in the range of 30 to 60 ° C.
(2) The adhesive layer of the B layer is a polyester having a glass transition temperature TgB in the range of -20 to 20 ° C and a melting point TmB in the range of 120 to 210 ° C.

Moreover, the preferable aspect of this invention is as follows. That is,
(1) The polyester of the A layer satisfies the following (A) and (B):
(A) It is comprised from the polyester which consists of a monomer composition containing 90 mol% or more of aromatic dicarboxylic acid components with respect to all the dicarboxylic acid components,
(B) A monomer containing ethylene glycol as an essential component and 90 mol% or more of a glycol component consisting of at least one selected from 1,3-propanediol and 1,4-butanediol with respect to all glycol components Consists of polyester made of composition.
(2) The polyester of the B layer satisfies the following (a) and (b):
(A) It is comprised from the polyester which consists of a monomer composition of the range of 60-90 mol% of aromatic dicarboxylic acid, and the range of 10-40 mol% of aliphatic dicarboxylic acid with respect to all the dicarboxylic acid components,
(B) With respect to all glycol components, ethylene glycol is in the range of 20 to 80 mol%, and at least one selected from 1,3-propanediol and 1,4-butanediol is 80 to 20 mol%. Composed of a polyester comprising a monomer composition contained in the range of
(3) The dimer content in the aliphatic dicarboxylic acid component is 70 to 90% by weight, and the trimer content is 10 to 30% by weight,
(4) the aliphatic dicarboxylic acid component is a dimer acid or a dimer acid derivative;
It is.
In addition, the decorative sheet of the present invention is characterized in that the laminated polyester sheet is laminated on the interior base material so that the layer A of the laminated polyester sheet becomes the outer surface.

  According to the present invention, it is possible to provide a laminated polyester sheet having excellent scratch resistance, stain resistance, chemical resistance, embossability, and thermal adhesiveness. The laminated polyester sheet obtained in the present invention can be suitably used for industrial materials and packaging materials that require moldability, heat resistance, chemical resistance, and thermal adhesiveness, and is particularly preferable for applications such as building materials and interiors. Can be used.

  The present invention satisfies the above-mentioned problems, that is, the basic required characteristics of a building material sheet and interior sheet such as scratch resistance, chemical resistance, embossability, and thermal adhesiveness, and is excellent in heat resistance and whitening resistance with time. As a result of diligent research on the laminated polyester sheet, and trying to compose the laminated polyester with a polyester in which the crystallinity or thermal characteristics of the polymer constituting each layer is controlled within a specific range, this problem can be solved at once. As a result, the present invention has been completed.

  In general, polyester is inferior in chemical resistance in an amorphous state and is often immersed in a solvent or the like. Therefore, when printing or wiping is performed using a solvent or the like, whitening may occur. In the amorphous state, scratch resistance is poor and scratches may remain. Furthermore, when the polyester having a low crystallization rate is rapidly cooled from the molten state, it becomes an amorphous state, and a transparent molded body is obtained. However, whitening occurs when the obtained molded product is left at a temperature of Tg or higher. This is because crystallization of the polyester has progressed and spherulites having a visible light size or more are generated. Further, when the glass transition temperature Tg of the polyester is below room temperature or near room temperature, when the crystallization speed of the polyester is low, crystallization (whitening) proceeds with time, and may not be preferred in some cases. . In order to prevent this phenomenon, it is necessary to increase the crystallization speed of the polyester. Polyesters represented by polybutylene terephthalate (PBT) have a very high crystallization rate, and when rapidly cooled from the molten state, a large amount of microcrystals already below the visible light size are generated, enabling transparent crystallization. . When transparent crystallization is achieved, not only the above-described whitening over time can be suppressed, but also chemical resistance, scratch resistance, handling properties and blocking resistance are improved. However, as the crystallization progresses, the moldability such as embossing is inferior, and it is difficult to achieve both chemical resistance, scratch resistance, whitening resistance with time and moldability.

  Therefore, the inventors of the present invention have made extensive studies, and in order to achieve both chemical resistance, scratch resistance, whitening resistance with time and formability, the sheet structure is a laminate, and the polymer constituting each layer thereof, It is composed of polyester whose crystallinity or thermal properties are controlled within a specific range.

  That is, the characteristic required for the layer (A layer) in which the said characteristic becomes favorable was discovered. That is, a polyester having a glass transition temperature TgA in the range of 40 to 70 ° C. and a crystallization parameter TcgA in the range of 30 to 60 ° C. was used. According to the A layer, it was found that the crystallinity can be controlled, the chemical resistance, the scratch resistance, the whitening resistance with time and the moldability can be compatible, and the above characteristics are excellent.

  When such a layer A is used on the surface side of a laminated sheet used as a protective sheet layer, since the crystallization parameter TcgA is 30 to 60 ° C., chemical resistance, scratch resistance, and whitening resistance over time can be exhibited. . Here, the crystallization parameter [Delta] TcgA is the difference between the crystallization temperature (Tc) and the glass transition temperature (Tg) observed in the temperature rising process of differential scanning calorimetry (DSC).

  Using this polyester, by controlling the sheet thickness after melt extrusion, cooling temperature, and controlling crystallinity, it is possible to produce microcrystals with a visible light size or less in the cooling process, and a molded product with excellent transparency In addition, it is excellent in chemical resistance, scratch resistance, and whitening resistance with time.

  Typical polymers of polyesters with a crystallization parameter ΔTcgA in the range of 30-60 ° C. include polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene adipate, polyethylene sebacate, polybutylene adipate, polybutylene sebacate, polybutylene naphthalate , And copolymers thereof can be used.

  The protective sheet layer A is a layer having moldability. Molding typified by embossing or the like is usually often heated to a temperature higher than the glass transition temperature Tg of the polymer for a certain time, molded into a required shape, and then cooled to a temperature lower than Tg. Therefore, the glass transition temperature TgA of the A layer having a molding function is required to be 40 to 70 ° C. Preferably, it is 45-70 degreeC. When TgA exceeds 70 ° C., it cannot be molded even if heated for a certain time. On the other hand, if it is less than 40 ° C., the room temperature becomes close to the glass transition temperature after molding, particularly when left in summer, etc., and therefore deformation is likely to proceed gradually.

  The polyester having a glass transition temperature TgA in the range of 40 to 70 ° C. and a crystallization parameter ΔTcgA in the range of 30 to 60 ° C. of the A layer of the present invention as a dicarboxylic acid, The aromatic dicarboxylic acid component is preferably composed of a polyester having a monomer composition containing 90 mol% or more. Polyester composed of a monomer composition containing, as a glycol component, ethylene glycol as an essential component and 90 mol% or more of at least one selected from 1,3-propanediol and 1,4-butanediol with respect to all glycol components It is preferable that it is comprised.

  In the case of the present invention, specific examples of the polyester used in the A layer include: a dicarboxylic acid component as an aromatic dicarboxylic acid; a glycol component as at least one selected from 1,3-propanediol and 1,4-butanediol; Polyester having a monomer composition containing a glycol component consisting of: polypropylene terephthalate and its copolymer or polybutylene terephthalate and its copolymer.

  Of course, the crystalline polyester may contain additives such as known crystal nucleating agents, antiblocking agents, slipping agents, antistatic agents, stabilizers, weathering agents, UV absorbers and pigments.

  In order to satisfy the scratch resistance, chemical resistance, moldability, whitening resistance with time, and thermal adhesiveness with a base material, which has been difficult to achieve with a single layer, the present invention has a laminated structure in which functions are separated into layers. This is a major feature. As described above, the A layer is a layer that achieves both chemical resistance, scratch resistance, whitening resistance with time, and moldability by using polyester with controlled crystallinity. The B layer is an adhesive layer that adheres to the substrate. In many cases, the molded sheet is used after being molded or bonded to a base material serving as a base during molding. Taking interior use such as furniture as an example, the base material usually includes a metal plate, a wooden board, an inorganic board board, and a plastic board. Therefore, the surface sheet needs to be bonded to the base material, usually heat-bonded, but currently available polyesters such as PET and PBT, polyolefins such as polypropylene, various kinds of ethylene-vinyl alcohol copolymers, etc. A single sheet is not preferable for thermal adhesion with a substrate. In order to have thermal adhesiveness, it is necessary to laminate the adhesive layer by coating or coextrusion. However, when the adhesive is laminated, the cost increases due to the increase in raw materials other than the sheet substrate, and the adhesive layer is laminated. If the sheet is recycled, there will be a problem in terms of quality such as foreign matter.

  In general, unstretched polyester sheets have a low elongation at break due to volume relaxation or enthalpy relaxation over time, and the sheet becomes brittle. For example, when the polyester is composed of a single film sheet, the elongation at break becomes several percent over time, and if the tension is applied in post-processing such as bonding to a base material or embossing, the sheet is easily torn and handling is poor. Become. The polyester that causes this phenomenon is a polyester that has a glass transition temperature Tg near room temperature and can be crystallized, and is produced by forming an amorphous sheet. This phenomenon progresses faster as the intrinsic viscosity (IV) of the polyester is lower and the sheet is thinner.

Therefore, the inventors of the present invention have made extensive studies and in order to improve the resistance to embrittlement over time,
As a layer constituting the laminated sheet, a layer made of a polymer which suppresses embrittlement with time and has excellent thermal adhesiveness is laminated.

  That is, when a B layer composed of amorphous polyester having a glass transition temperature TgB in the range of −20 to 20 ° C. and a melting point TmB in the range of 120 to 210 ° C. is provided, the embrittlement with time is suppressed. And it discovered that the laminated sheet excellent in thermal adhesiveness was provided. When the glass transition temperature TgB of the polyester constituting the B layer is less than −20 ° C. and the melting point TmB is less than 120 ° C., the molded product (laminated sheet) obtained from the polyester is likely to be sticky and blocked. In addition, when the glass transition temperature TgB exceeds 20 ° C. and the melting point TmB exceeds 210 ° C., the resulting molded product is not preferable from the viewpoint of resistance to embrittlement with time and thermal adhesiveness.

  The amorphous polyester having a glass transition temperature TgB in the range of −20 to 20 ° C. and a melting point TmB in the range of 120 to 210 ° C. constituting the B layer in the present invention has a hard segment as a dicarboxylic acid component. It is comprised from the aromatic dicarboxylic acid component which comprises, and the aliphatic dicarboxylic acid which comprises a soft segment.

  The aromatic dicarboxylic acid component constituting the hard segment is formed from an aromatic dicarboxylic acid and an ester-forming derivative thereof. Specifically, for example, isophthalic acid, terephthalic acid, diphenyl-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalene 2,7-dicarboxylic acid, naphthalene 1,5-dicarboxylic acid, diphenoxyethane Examples include 4-4′-dicarboxylic acid, diphenylsulfone-4, 4′-dicarboxylic acid, diphenyl ether-4, 4′-dicarboxylic acid, and ester-forming derivatives thereof. Of these, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and ester-forming derivatives thereof are preferable. These aromatic dicarboxylic acid components may be used alone or in combination of two or more.

  The amount of the aromatic dicarboxylic acid component is preferably 60 to 90 mol% of the total dicarboxylic acid component. More preferably, it is 65-90 mol%, Most preferably, it is 70-90 mol%. If the amount of the aromatic dicarboxylic acid component is less than 60 mol%, the molded product obtained from this polyester is not preferable because it causes adhesion, blocking, etc., and the handleability tends to deteriorate. On the other hand, if it exceeds 90 mol%, it is not preferable from the viewpoint of resistance to embrittlement with time and thermal adhesiveness.

  The aliphatic dicarboxylic component constituting the soft segment is derived from a saturated fatty acid and an unsaturated fatty acid. Examples of the saturated fatty acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like. Unsaturated fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, valmitic acid, heptadecanoic acid, stearic acid, oleic acid, elaidic acid , Linoleic acid, linolenic acid, stearoleic acid, ricinoleic acid, ricinoelaidic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, brassic acid, erucic acid, tricosanoic acid, lignoceric acid and the like. In view of having a soft segment, an unsaturated fatty acid is preferable, and an unsaturated fatty acid having 10 to 30 carbon atoms is preferable. Particularly preferred are dimerized fatty acids obtained by dimers of unsaturated fatty acids or ester-forming derivatives thereof.

  In this dimerization reaction of unsaturated fatty acid, a trimer is produced together with the dimer, and therefore the dimer, trimer and monomer are contained in the aliphatic dicarboxylic acid derivative obtained by the dimerization reaction. It is. When this aliphatic dicarboxylic acid derivative is purified by distillation several times, and a high-purity aliphatic dicarboxylic acid derivative having a dimer amount of 95% or more, more preferably 98% or more is used, a polyester having good color tone can be obtained. Although the cost of the aliphatic dicarboxylic acid derivative is remarkably increased by the distillation process, in order to achieve both the color tone and cost performance of the polyester, the dimer and trimer in the aliphatic dicarboxylic acid derivative The ratios are preferably 70 to 90% by weight and 10 to 30% by weight, respectively.

  The aliphatic dicarboxylic acid derivative used in the production of the polyester constituting the B layer of the present invention has an unsaturated bond produced by the dimerization reaction. You may use after reducing by reaction. However, particularly when heat resistance, weather resistance, and transparency are required, it is preferable to use a dimerized fatty acid in which unsaturated bonds are eliminated by hydrogenation.

  As the dimerized unsaturated fatty acid that can be used in the production of the polyester, dimer acid which is a dimerized fatty acid having 36 carbon atoms and an ester-forming derivative thereof are preferable. The dimer acid is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as linoleic acid and linolenic acid. For example, Pripol (registered trademark) ("PRIPOL") from Unikema International, or these Various ester forming derivatives are commercially available. One or more of the above compounds may be used in combination.

  In the polyester constituting the B layer of the present invention, the amount of the aliphatic dicarboxylic acid is preferably 10 to 40 mol%, more preferably 10 to 35%, further preferably 10 to 35%, based on the total dicarboxylic acid component. 30 mol%. When the amount of the aliphatic dicarboxylic acid exceeds 40 mol%, the molded product obtained from the resulting solution becomes too soft, causing sticking and blocking, and the handleability tends to deteriorate. If the amount of the aliphatic dicarboxylic acid is less than 10 mol%, the molded product obtained therefrom becomes hard, which is not preferable from the viewpoint of resistance to embrittlement with time and thermal adhesiveness.

  The polyester constituting the B layer of the present invention includes, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-butane as a glycol component. Diol, 1,4-butanediol, 1,2-butanediol, 1,5-pentyl glycol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 1,6 -Hexanediol, 2-methyl-2-ethyl-1,3-propanediol, 1,8-octanediol, 1,10-decanediol, 1,3-cyclobutanediol, 1,3-cyclobutanedimethanol, 1, Examples include 3-cyclopentanedimethanol and 1,4-cyclohexanedimethanol. Among these, at least one selected from ethylene glycol, 1,3-propanediol, and 1,4-butanediol is preferable. Ethylene glycol is an essential component, and 1,3-propanediol and 1, More preferably, at least one selected from 4-butanediol is selected. It is preferable to select a multi-component glycol because when only one glycol component is used, the polymer chain is less disturbed and the crystallinity may be too high. This is because the crystallinity can be controlled.

  When designing a polyester satisfying the glass transition temperature TgB in the range of −20 ° C. to 20 ° C. and the melting point TmB in the range of 120 ° C. to 210 ° C. in the polyester constituting the B layer of the present invention, From the viewpoint of controlling properties, the glycol component is an essential component of ethylene glycol, and is a polyester comprising 90 mol% or more of a monomer composition of at least one selected from 1,3-propanediol and 1,4-butanediol. Preferably, it is configured. More preferably, ethylene glycol is in the range of 20 to 80 mol%, and at least one selected from 1,3-propanediol and 1,4-butanediol is 80 to 20 mol based on the total glycol component. % Of the monomer composition is preferably contained.

  In the polyester of the present invention, in addition to the above components, other components may be copolymerized within a range not impairing the object of the present invention, or a resin composed of other components may be mixed. Examples of copolymerizable acid components include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid trimellitic acid, trimesic acid, trimellitic acid Trimesic acid, etc., or ester derivatives thereof, p-oxybenzoic acid, p-hydroxymethylbenzoic acid, or ester derivatives thereof as hydroxycarboxylic acid components, and 1,12-dodecanediol, diethylene glycol, as glycol components, Polyoxyalkylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, spiroglycol, or bisphenol A, bisphenol S and their ethylene oxide De adducts, trimethylolpropane and the like.

  In the case of the polyester of the present invention, the melt viscosity is preferably 1000 to 3000 poise at 250 ° C., more preferably 1300 to 2300 poise. When the melt viscosity of the polyester exceeds 3000 poise, when the polyester is extruded into a sheet or the like, the extruded state may not be stable, and a non-uniform film thickness may be provided. Furthermore, the partially thickened portion may be whitened and spotted. Moreover, when the melt viscosity is less than 1000 poise, film formation may be difficult due to insufficient viscosity.

  The method for producing the above-described polyester of the present invention is not particularly limited, and can be produced by a normal polyester polymerization method. For example, a method of directly copolymerizing a glycol component, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid derivative from a composition containing the specific range described above may be used, or two or more kinds of polymers and / or Alternatively, the copolymer may be melt-kneaded in an extruder so as to have the specific polymerization composition described above.

  The latter method includes an aromatic polyester composed of an aromatic dicarboxylic acid and a glycol component, and an aliphatic-aromatic polyester copolymer composed of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid derivative and a glycol component. Examples thereof include a method of melting and kneading in an extruder so as to obtain the above-described specific polymerization composition. Polyester with only the cost advantage of being able to use general-purpose aromatic polyesters such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), etc., and only changing the mixing amount of aromatic polyester and copolymer The component contained therein can be freely controlled, and from the viewpoint of handling properties, an aromatic polyester and an aliphatic-aromatic polyester copolymer are preferably melted and kneaded in an extruder to obtain the above-described specific polymerization composition. Aromatic polyester mainly composed of “terephthalic acid and / or isophthalic acid, ethylene glycol, and at least one selected from the group of 1,3-propanediol and 1,4-butanediol components”, Is mainly "Terefta An aliphatic-aromatic polyester composed of an acid, a fatty acid or a derivative thereof, and at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol is melt-kneaded in an extruder. The above-mentioned method of making the specific polymerization composition is preferred, the constituent component is mainly an aromatic polyester composed of “terephthalic acid and / or isophthalic acid and ethylene glycol”, and the constituent component is mainly “terephthalic acid and a fatty acid or a derivative thereof. And an aliphatic-aromatic polyester copolymer consisting of “1,4-butanediol” and melt-kneading in an extruder to obtain the above-mentioned specific polymerization composition is more preferable.

  In order to improve the melt viscosity of the polyester obtained by copolymerization and the transparency of the polyester resin molded article, it is preferable to add the following compatibilizing agent at the time of copolymerization or resin mixing. Examples of the compatibilizer include compounds having reactivity with hydroxy groups and / or carboxyl groups, such as diglycidyl hexahydrophthalate, diglycidyl terephthalate, diglycidyl phthalate, bisphenol S diglycidyl ether, and polyethylene glycol diglycidyl ether. Glycidyl compounds, various oxazolines such as 1,4-phenylenebisoxazoline and 1,3-phenylenebisoxazoline, various ester compounds of various fatty acids such as stearic acid, oleic acid and lauric acid and polyether, and hydrochloric acid, sulfuric acid, nitric acid, Although organic acids, such as p-toluenesulfonic acid, are mentioned, it is preferable to use bisoxazoline or p-toluenesulfonic acid especially. The mechanism of improving the melt viscosity or transparency by adding the above compound is not necessarily clear.

  Further, the present invention is not restricted by a specific mechanism or hypothesis, but for example, it can be explained by the following model.

[Bisoxazoline addition effect]
By adding bisoxazoline, which is a bifunctional compound, the carboxylic acid terminals in the polyester chain react with each other, contributing to an increase in molecular weight, which is one of the main factors for improving the melt viscosity. In addition, when an aromatic polyester and an aliphatic-aromatic polyester copolymer composed of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid derivative and a glycol component are melt-kneaded to obtain a polyester or a sheet thereof, bisoxazoline Two types of functional groups are added to the carboxylic acid ends of different types of polymers (for example, aromatic polyester and aliphatic-aromatic polyester copolymer) to form a block copolymer. Increases compatibility and improves transparency.

[Organic acid addition effect]
When melt-kneading an aromatic polyester and an aliphatic-aromatic polyester copolymer to produce a polyester or its sheet or molded product, the transesterification reaction between different polymers is accelerated by the acid catalytic effect of the organic acid. In addition, the formation of polyester is promoted, and the transparency is improved by homogenizing the polymer chain.

  The addition amount in the case of adding the compatibilizing agent shown above to the polyester may be any amount as long as the melt viscosity reaches the desired viscosity level and exhibits the desired transparency, and is in the range of 0.1 to 5% by weight. Is preferred. Moreover, it is preferable that the addition amount in the case of adding a compatibilizer to the said polyester resin composition is the range of 0.1 to 5 weight%.

  The sheet of the present invention is a sheet obtained by adding various particles and additives to the above-described polyester as necessary, and then forming a film by a usual method. Accordingly, it is produced by stretching or heat treatment.

  The particles to be added to the sheet are appropriately selected depending on the purpose and application, and are not particularly limited as long as the effects of the present invention are not impaired. Inorganic particles, organic particles, cross-linked polymer particles, internal parts formed in the polymerization system Examples thereof include particles. Two or more kinds of these particles may be added. From the viewpoint of the mechanical properties of the polyester resin composition, the amount of such particles added is preferably 0.01 to 10% by weight, and more preferably 0.02 to 1% by weight.

  Moreover, the number average particle diameter of the particle to add becomes like this. Preferably it is 0.001-10 micrometers, More preferably, it is 0.01-2 micrometers. When the number average particle size is in such a preferable range, defects in the resin composition and the sheet are less likely to occur, and it is difficult to cause deterioration in transparency and moldability.

  The inorganic particles are not particularly limited, but various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, various composite oxides such as kaolin and talc, lithium phosphate, calcium phosphate Fine particles comprising various phosphates such as magnesium phosphate, various oxides such as aluminum oxide, silicon oxide, titanium oxide and zirconium oxide, various salts such as lithium fluoride, and the like can be used.

  As the organic particles, fine particles made of calcium oxalate, terephthalate such as calcium, barium, zinc, manganese, magnesium and the like are used. Examples of the crosslinked polymer particles include fine particles made of a vinyl monomer such as divinylbenzene, styrene, acrylic acid or methacrylic acid, or a copolymer. In addition, organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.

  As the internal particles generated in the polymerization system, particles generated by a known method in which an alkali metal compound, an alkaline earth metal compound, or the like is added to the reaction system and a phosphorus compound is further added may be used.

  In the sheet of the present invention, as long as the effects of the present invention are not impaired, known additives such as flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, plastics are used as necessary. An appropriate amount of an agent, a tackifier, an organic lubricant such as a fatty acid ester or wax, an antifoaming agent such as polysiloxane, or a coloring agent such as a pigment or dye can be blended.

  As a sheet configuration, it is necessary to have at least a two-layer configuration of A / B, but new functions such as scratch resistance, slipperiness, flame retardancy, adhesiveness, tackiness, heat resistance, and weather resistance are provided on the surface. A layer for imparting the thickness may be further laminated, and the lamination thickness ratio of each layer can be arbitrarily set.

  The sheet of the present invention may be an unstretched sheet or a stretched sheet. The stretched sheet may be either a uniaxially stretched sheet stretched in either the longitudinal direction or the width direction of the sheet, or a biaxially stretched sheet stretched in both the longitudinal direction and the width direction of the sheet.

  Moreover, it is preferable to set it as a stretched film from a viewpoint of whitening-proof whitening, and it is more preferable to set it as a biaxially stretched film. The plane orientation coefficient in the case of a biaxially stretched film is preferably 0.0030 to 0.150, more preferably 0.050 to 0.140, from the viewpoint of preventing whitening during processing and maintaining workability. Particularly preferred is 0.080 to 1.130.

Here, the plane orientation coefficient (fn) is a film longitudinal direction, width direction, and thickness direction refractive index (Nx, Ny, respectively) measured using an Abbe refractometer or the like by a method defined in JIS-K7105 (1981). , Nz) is a value calculated by the following equation.
-Planar orientation coefficient: fn = (Nx + Ny) / 2-Nz.

  Further, the film of the present invention has a thermal shrinkage ratio in at least one direction at a molding temperature in the range of −10 to 10% from the viewpoint of suppressing thermal adhesiveness and workability, particularly sheet wrinkling during processing. Is preferred. More preferably, the heat shrinkage rate is in the range of −5 to + 5%. When the thermal shrinkage is within this range, good workability can be imparted without causing problems such as the sheet surface swelling to impair the appearance, peeling from the base material, or distorting printing.

  B layer may be laminated by sheet lamination or extrusion lamination. The thickness of each layer can be freely set according to the intended use. The thickness of the laminated polyester sheet is usually in the range of 0.5 to 1000 μm, preferably 1 to 500 μm, more preferably 5 to 200 μm from the viewpoint of film formation stability. As for the thickness of each layer, A layer 0.1-200 micrometers and B layer 0.1-100 micrometers are preferable.

  The sheet of the present invention can be subjected to surface treatment such as corona discharge treatment to improve thermal adhesiveness and printability as necessary. Various coatings may be applied, and the type, coating method, and thickness of the coating compound are not particularly limited as long as the effects of the present invention are not impaired. Furthermore, it can be used after being subjected to molding processing such as embossing, printing, or the like, if necessary.

  The composite sheet of the present invention can be used as various industrial materials and packaging materials that require easy moldability. The laminated polyester sheet can be used by being bonded to a base material such as metal, wood, paper, resin sheet or resin plate so that the A layer of the laminated polyester sheet is arranged on the outer surface, preferably flooring, general furniture, kitchen It is preferable to bond to interior base materials such as furniture and office furniture.

  Specific applications include applications in which conventional flexible sheets and easily molded sheets have been used, such as packaging sheets, wrap sheets, stretch sheets, building materials such as partition sheets and plywood decorative sheets, and interior sheets. However, the present invention is not limited to this.

  Hereinafter, the present invention will be described in detail by way of examples. Various characteristics were measured and evaluated by the following methods.

(1) Intrinsic viscosity of polyester Polyester was dissolved in orthochlorophenol and measured at 25 ° C.

(2) Melt viscosity of polyester The polyester was dried at 130 to 150 ° C under reduced pressure for 5 hours or more and then measured at 250 ° C using a melt index.

(3) Composition ratio (content) of monomer, dimer and trimer in fatty acid carboxylic acid (derivative)
The composition was analyzed by high performance liquid chromatography, and the composition ratio (content) was determined from the peak area of each component.

(4) Thermal properties (DSC) of polyester {glass transition temperature Tg (° C), crystallization temperature Tc (° C), melting point Tm (° C), crystallization parameter ΔTcg (° C)}
Using a differential scanning calorimeter DSCII type manufactured by Seiko Instrument Co., Ltd., a sample 5 mg was heated at a rate of 10 ° C./min to increase the glass transition temperature (Tg), the crystallization temperature (Tc) at the time of temperature increase, and the melting point (Tm ) Was measured. The crystallization parameter ΔTcg was determined by the following equation.
ΔTcg = Tmc−Tc.

(5) Film-forming stability The stability during film-forming was evaluated according to the following criteria. ○ and Δ are suitable as satisfying the invention of the present application.
○: A film that can be stably formed with a constant discharge rate.
Δ: Discharge is temporarily unstable, but there is almost no problem in film forming properties.
X: The discharge amount is clearly unstable and stable film formation is difficult.

(6) Transparency of sheet (haze)
Using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., the haze was measured at 5 points, the average value was obtained, and the transparency of the sheet was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies the invention of this application.
○: The haze value is less than 5%.
Δ: Haze value in the range of 5 to 10%.
X: The haze value exceeds 10%.

(7) Whitening resistance of sheet with time With respect to the sheet after being put into a 40 ° C. gear oven for one week, the haze value was tested using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. The points were measured, the average value was obtained, and the whitening resistance over time of the sheet was evaluated according to the following criteria. ○ and Δ are suitable as satisfying the invention of the present application.
○: The haze value is less than 5%.
Δ: Haze value in the range of 5 to 10%.
X: The haze value exceeds 10%.

(8) Scratch resistance of the sheet (pencil method)
The sheet surface (A surface) was tested twice according to JIS K5600 (1999) scratch hardness (pencil method). When no scar was generated, the test was repeated with the hardness scale raised until the scratch was generated, and when the scratch was generated, the test was repeated with the hardness scale lowered until no scratch was generated. The hardness of the hardest pencil with no scars was taken as the pencil hardness. When the two test results are different, the test was performed five times, and the pencil hardness was the highest. The scratch resistance of the sheet was evaluated from the pencil hardness according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○: The pencil hardness is in the range of H to 6H.
Δ: Pencil hardness is F or HB.
X: The thing whose pencil hardness is the range of 6B-B.

(9) Chemical resistance of sheet 3 ml of a stock solution of chlorine detergent (Kao Co., Ltd .: Kitchen Hiter (registered trademark)) was dropped on the sheet surface (A layer), and the temperature was 23 ° C. and humidity was 65% RH. After being left for a period of time, it was carefully wiped with tissue paper, further wiped with water, and then wiped with air. The test number was 2, and when the test results of the two points were different, the test number was 5, and the most test results were used to evaluate the chemical resistance of the sheet according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○: There is no hole in the sheet surface, no tearing, and no deformation.
Δ: Perforated, torn, and hardly deformed on the sheet surface.
X: The sheet surface is perforated, torn, and deformed.

(10) Resistance to embrittlement of sheet over time (elongation at break)
The sheet was allowed to stand at a temperature of 23 ° C. and a humidity of 65% RH for 1 week, and then measured at 23 ° C. using Tensilon manufactured by Orientec Co., Ltd. For a sample having a width of 10 mm and a sample length of 100 mm after keeping the film at the measurement temperature for 30 seconds, the elongation at break (%) in the film longitudinal direction and the width direction was measured at 10 points at a tensile rate of 200 mm / min. The value was obtained, and the embrittlement resistance with time of the sheet was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○: The elongation at break is 100% or more in both the longitudinal direction and the width direction of the film,
(Triangle | delta): The thing whose elongation at break is 10 to 100% in the longitudinal direction and the width direction of the film,
X: The elongation at break is less than 10% in both the longitudinal direction and the width direction of the film.

(11) Sheet formability (embossing)
The sheet was passed through an embossing roll while preheating at 120 ° C., and the unevenness on the surface of the embossing roll was transferred to the sheet. The embossing roll surface was observed using an ultra-deep shape measuring microscope (manufactured by Keyence Co., Ltd.), and the area (S1 (i)) of the top surface of the convex portion for one arbitrary convex portion was determined. Subsequently, the concave portion on the surface of the sheet on which the convex portion observed above was transferred was observed with an ultra-depth shape measuring microscope, and the area (S2 (i)) of the bottom surface of the concave portion of the sheet after transfer was obtained. The same operation is performed at arbitrary 10 locations (i = 1 to 10), and the average values at 10 locations are defined as S1 and S2, respectively. The ratio of the average values S1 and S2 ((S2 / S1) × 100) was defined as “transfer rate”, and the formability of the sheet was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
A: The transfer rate exceeds 70%.
Δ: Transfer rate in the range of 40 to 70%.
X: Transfer rate is less than 40%.

(12) Thermal adhesiveness with substrate The sheet is cut into 3 cm × 10 cm (width direction × longitudinal direction), and the B layer side of the sheet is bonded to the substrate (3 cm × 10 cm (width direction × longitudinal direction)). After pressure bonding at a temperature of 9.8 ° C. for 2 seconds at a pressure of 9.8 × 10 ⁴ N / m ² , the peel strength (N) between the sheet and the base material was adjusted to a temperature of 23 The number of tests was measured at 5 ° C., the average value was determined, and the thermal adhesion of the sheet was evaluated according to the following criteria. As the base material, a vinyl chloride sheet (Belfan (registered trademark) T-305 (200 μm) manufactured by Tatsuta Chemical Co., Ltd.) was used.
○: The peel strength exceeds 5 × 10 ⁷ N.
△: Peeling strength ^{1 × 10 7 ~5 × 10 7} N in the range of things.
X: The peel strength is less than 1 × 10 ⁷ N.

(13) Comprehensive evaluation Practicality as a sheet for building materials and an interior sheet for film-forming stability, transparency, whitening resistance over time, scratch resistance, chemical resistance, moldability, thermal adhesion, and resistance to embrittlement over time About, the thing which was excellent was evaluated as ◯, the slightly inferior one as Δ, and the inferior one as ×.

[Polymerization of aromatic polyester]
{Synthesis of Polyester 1 (PET)}
To a mixture of 95.3 parts by weight of dimethyl terephthalic acid and 54.7 parts by weight of ethylene glycol, 0.09 part by weight of magnesium acetate and 0.03 part by weight of diantimony trioxide are added, and the temperature is raised by heating in a conventional manner. A transesterification reaction was performed. Next, 0.026 part by weight of trimethyl phosphate was added to the transesterification reaction product, and then transferred to a polycondensation reaction tank. Next, the reaction system was gradually depressurized while being heated and heated, and polymerization was performed at 290 ° C. under a reduced pressure of 1.33 × 10 ² Pa or less to obtain polyester 1 having an intrinsic viscosity of 0.69.

{Synthesis of Polyester 2 (PBT)}
To a mixture of 81.8 parts by weight of dimethyl terephthalic acid and 68.2 parts by weight of 1,4-butanediol, 0.05 part by weight of tetrabutyl titanate, IRGANOX® 1010 (Ciba Specialty Chemicals) 0. 02 parts by weight was added and the temperature was finally raised to 210 ° C. to conduct a transesterification reaction. After transesterification, 0.01 part by weight of trimethyl phosphate, 0.07 part by weight of tetrabutyl titanate, and 0.03 part by weight of IRGANOX (registered trademark) 1010 were added. The temperature was gradually raised and the pressure was reduced, and finally a polycondensation reaction was performed at 245 ° C. and 1.33 × 10 ² Pa or less to obtain polyester 2 having an intrinsic viscosity of 1.20.

{Synthesis of Polyester 3 (PPT)}
To a mixture of 87.9 parts by weight of dimethyl terephthalate and 62.1 parts by weight of 1,3-propanediol, 0.06 part by weight of tetrabutyl titanate was added, and finally the temperature was raised to 220 ° C. to conduct a transesterification reaction. . After transesterification, 0.05 part by weight of trimethyl phosphate and 0.04 part by weight of tetrabutyl titanate were added. The temperature was gradually raised and the pressure was reduced, and finally a polycondensation reaction was performed at 260 ° C. and 1.33 × 10 ² Pa or less to obtain Polyester 3 having an intrinsic viscosity of 0.80.

{Synthesis of Polyester 4 (PET / I 12 mol%)}
Charge 67.1 parts by weight of dimethyl terephthalate, 28.1 parts by weight of dimethyl isophthalate, 54.8 parts by weight of ethylene glycol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX (registered trademark) 1010FP, and 150 ° C. The mixture was subjected to a transesterification according to a conventional method while raising the temperature from 210 to 210 ° C., and then 0.042 parts by weight of trimethyl phosphoric acid was added, and 10 minutes later, 0.055 parts by weight of tetrabutyl titanate, IRGANOX (registered trademark) 1010FP0. After adding 022 parts by weight, the reaction system was transferred to a polycondensation reaction tank, and the reaction system was gradually depressurized while being heated and heated, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1.33 × 10 ² Pa. Polyester 4 having an intrinsic viscosity of 0.70 and 12 mol% of isophthalic acid was obtained.

{Synthesis of Polyester 5 (PET / I 17.5 mol%)}
Charge 57.7 parts by weight of dimethyl terephthalate, 37.5 parts by weight of dimethyl isophthalate, 54.8 parts by weight of ethylene glycol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX (registered trademark) 1010FP, and 150 ° C. The mixture was subjected to a transesterification according to a conventional method while raising the temperature from 210 to 210 ° C., and then 0.042 parts by weight of trimethyl phosphoric acid was added, and 10 minutes later, 0.055 parts by weight of tetrabutyl titanate, IRGANOX (registered trademark) 1010FP0. After adding 022 parts by weight, the reaction system was transferred to a polycondensation reaction tank, and the reaction system was gradually depressurized while being heated and heated, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1.33 × 10 ² Pa. A polyester 5 having 17.5 mol% of isophthalic acid having an intrinsic viscosity of 0.69 was obtained.

[Polymerization of aromatic-aliphatic copolymer polyester]
(Synthesis of copolymer polyester 1)
Charge 47.9 parts by weight of dimethyl terephthalate, 17.8 parts by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX (registered trademark) 1010FP, and increase from 150 ° C. to 210 ° C. Transesterification was carried out in accordance with a conventional method while warming, 0.042 parts by weight of trimethyl phosphoric acid was added, and after 10 minutes, 0.055 parts by weight of tetrabutyl titanate, 0.022 parts by weight of IRGANOX (registered trademark) 1010FP, 48.8 parts by weight of dimer acid (PRIPOL (registered trademark) 1025: made by Unikema) heated to 50 ° C./35.5 parts by weight of 1,4-butanediol was added. After the can internal temperature returned to 210 ° C., the mixture was stirred for 30 minutes and then transferred to a polymerization reaction tank, and a polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 245 ° C. and 1.33 × 10 ² Pa or less to obtain a copolymer polyester 1 having an intrinsic viscosity of 0.81 and 25 mol% of dimer acid.

(Synthesis of copolymer polyester 2)
Charge 73.6 parts by weight of dimethyl terephthalate, 23.4 parts by weight of 1,3-propanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX (registered trademark) 1010FP, and increase the temperature from 150 ° C to 210 ° C. Transesterification was carried out in accordance with a conventional method while warming, 0.042 parts by weight of trimethyl phosphoric acid was added, and after 10 minutes, 0.055 parts by weight of tetrabutyl titanate, 0.022 parts by weight of IRGANOX (registered trademark) 1010FP, A dimer acid (PRIPOL (registered trademark) 1025: made by Unikema Corp.) 43.3 parts by weight / 1,3-propanediol 26.6 parts by weight mixed slurry heated to 50 ° C. was added. After the can internal temperature returned to 210 ° C., the mixture was stirred for 30 minutes and then transferred to a polymerization reaction tank, and a polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 245 ° C. and 1.33 × 10 ² Pa or less to obtain a copolymer polyester 1 having an intrinsic viscosity of 0.81 and 25 mol% of dimer acid.

(Synthesis of copolymer polyester 3)
Dimethyl terephthalate 56.0 parts by weight, ethylene glycol 8.3 parts by weight, 1,4-butanediol 11.6% by weight, tetrabutyl titanate 0.04 parts by weight, IRGANOX 1010FP 0.016 parts by weight, Transesterification was carried out according to a conventional method while raising the temperature to 0 ° C., and then 0.042 parts by weight of trimethyl phosphoric acid was added, and after 10 minutes, 0.055 parts by weight of tetrabutyl titanate and IRGANOX (registered trademark) 1010FP0. 022 parts by weight, dimer acid preheated to 50 ° C. (PRIPOL (registered trademark) 1025: made by Unikema) 42.9 parts by weight / 1,4-butanediol 23.4 parts by weight / ethylene glycol 7.8 parts by weight After the slurry returned to 210 ° C, the slurry was stirred for 30 minutes. The process proceeds to the polymerization reaction vessel and subjected to polycondensation reaction according to a conventional method. Ultimately 245 ° C., subjected to polycondensation reaction at 1.33 × ¹⁰ 2 Pa or less, the intrinsic viscosity 0.80 dimer acid 15 mol% of Copolyester 3 was obtained.

(Synthesis of copolymer polyester 4)
A mixture of 63.3 parts by weight of dimethyl terephthalate, 15.2 parts by weight of ethylene glycol, 12.5% by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX 1010FP was charged at 150 to 210 ° C. Transesterification was carried out according to a conventional method while raising the temperature to 0 ° C., and then 0.042 part by weight of trimethyl phosphoric acid was added. After 10 minutes, 0.055 part by weight of tetrabutyl titanate and IRGANOX (registered trademark) 1010FP0.022 3 parts by weight of dimer acid (PRIPOL (registered trademark) 1098: manufactured by Unikema) 34.2 parts by weight / 1,4-butanediol 18.7 parts by weight / ethylene glycol 6.2 parts by weight mixed slurry previously heated to 50 ° C. Was added. After the can internal temperature returned to 210 ° C., the mixture was stirred for 30 minutes and then transferred to a polymerization reaction tank, and a polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 245 ° C. and 1.33 × 10 ² Pa or less to obtain a copolymer polyester 4 having an intrinsic viscosity of 0.80 and a dimer acid of 15 mol%.

(Synthesis of copolymer polyesters 5 and 7)
Copolyesters 5 and 7 listed in Table 1 were synthesized in the same manner as the copolyester 4.

(Synthesis of copolymer polyester 6)
Copolyester 6 listed in Table 1 was synthesized in the same manner as copolyester 3.

  Table 1 shows the compositions of polyesters and copolymerized polyesters used in Examples and Comparative Examples.

In Table 1, the abbreviations used are shown below.
DMT: terephthalic acid DMI: isophthalic acid C36: dimer acid (main chain carbon number 36)
C37: Dimer acid (main chain carbon number: 37)
C38: Dimer acid (main chain carbon number 38)
EG: ethylene glycol PG: 1,3-propanediol BG: 1,4-butanediol (Example 1)
Vent-type bi-directional twin-screw extruder A (2 vent portions, L / D = 45) in which a mixture of 50% by weight of polyester 2 and 50% by weight of polyester 5 is set at a cylinder temperature of 260 ° C. The polyester B is fed to the bent type bi-directional twin screw extruder B (two vents, L / D = 45) set to 230 ° C., and the die temperature is set to 230 ° C. The sheet was guided to the two-layer T die die, extruded into a sheet shape, closely contacted with a casting drum by an electrostatic application method, and solidified by cooling to obtain an unstretched sheet (A layer / B layer thickness ratio = 30/10 μm). Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Example 2)
A non-stretched sheet (A layer) in the same manner as in Example 1 except that 50% by weight of polyester 3 and 50% by weight of polyester 4 were used as the polyester for layer A, and copolymer polyester 2 was used as the polyester for layer B. / B layer thickness ratio = 25/25 μm). Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Example 3)
A non-stretched sheet (as in Example 1) except that 50% by weight of polyester 4 and 50% by weight of copolyester 6 were used as the polyester for layer A, and copolyester 3 was used as the polyester for layer B. A layer / B layer thickness ratio = 70/30 μm). Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

Example 4
A non-stretched sheet (layer A) in the same manner as in Example 1 except that the polyester of layer A was a mixture of 40% by weight of polyester 3 and 60% by weight of polyester 5 and the polyester of layer B was copolymerized polyester 4. / B layer thickness ratio = 40/10 μm). Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Example 5)
As the polyester of the A layer, a mixture of 60% by weight of polyester 2 and 40% by weight of polyester 5 was used, and as the polyester of the B layer, a mixture of 25% by weight of polyester 1 and 75% by weight of the copolyester 5 was used. An unstretched sheet (A layer / B layer thickness ratio = 40/20 μm) was produced in the same manner as in Example 1. Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Example 6)
A non-stretched sheet (A layer) in the same manner as in Example 1 except that the polyester of the A layer was a mixture of 20% by weight of polyester 2 and 80% by weight of polyester 5 and the polyester of the B layer was a copolymer polyester 4. / B layer thickness ratio = 35/35 μm). Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Comparative Example 1)
As the polyester of layer A, the polyester 2 (50% by weight) and polyester 5 (50% by weight) mixture of Example 1 was changed to polyester 1 (100% by weight), and as the polyester of layer B, the polyester of Example 1 was used. Example 1 except that the polymerization polyester 1 (100 wt%) was changed to polyester 5 (100 wt%), the extrusion temperatures of the A layer and the B layer were changed to 280 ° C. and 260 ° C., respectively, and the die temperature was changed to 260 ° C. Similarly, an unstretched sheet (A layer / B layer thickness ratio = 25/25 μm) was produced. Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Comparative Example 2)
As the polyester of layer A, the polyester 2 (50% by weight) and polyester 5 (50% by weight) mixture of Example 1 was changed to a mixture of polyester 1 (50% by weight) and polyester 5 (50% by weight). As the polyester of the layer, the copolymerized polyester 1 (100% by weight) of Example 1 was changed to polyester 4 (100% by weight), the extrusion temperatures of the A layer and the B layer were 260 ° C. and 260 ° C., respectively, and the die temperature was 260 ° C. An unstretched sheet (A layer / B layer thickness ratio = 40/10 μm) was produced in the same manner as in Example 1 except that the temperature was changed to ° C. Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Comparative Example 3)
As the polyester of layer A, the polyester 2 (50% by weight) and polyester 5 (50% by weight) mixture of Example 1 was changed to a mixture of polyester 1 (50% by weight) and polyester 2 (50% by weight). As the polyester of the layer, the copolymerized polyester 1 (100% by weight) of Example 1 was changed to the copolymerized polyester 5 (100% by weight), and the extrusion temperatures of the A layer and the B layer were respectively set to 260 ° C. and 250 ° C. An unstretched sheet (A layer / B layer thickness ratio = 50/20 μm) was produced in the same manner as in Example 1 except that the temperature was changed to 250 ° C. Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

(Comparative Example 4)
As the polyester of layer A, the polyester 2 (50% by weight) and polyester 5 (50% by weight) mixture of Example 1 was changed to polyester 2 (100% by weight), and as the polyester of layer B, the polyester of Example 1 Implemented except that the polymerization polyester 1 (100% by weight) was changed to the copolymerized polyester 7 (100% by weight), and the extrusion temperatures of the A layer and B layer were changed to 260 ° C and 250 ° C, respectively, and the die temperature was changed to 250 ° C. In the same manner as in Example 1, a non-stretched sheet (A layer / B layer thickness ratio = 40/20 μm) was produced. Table 2 shows the thermal characteristics of each layer polymer, and Table 3 shows the characteristics of the produced sheet.

  In the sheets obtained in Examples 1 to 3, the glass transition temperature TgA of the protective sheet layer of layer A is in the range of 40 to 70 ° C., the crystallization parameter ΔTcg is in the range of 30 to 60 ° C., and the glass of the adhesive layer of layer B When the transition temperature TgB is in the range of -20 to 20 ° C. and the melting point TmB is in the range of 120 to 210 ° C., transparency, whitening resistance over time, scratch resistance, chemical resistance, embrittlement resistance over time, moldability, heat The adhesiveness was also excellent. The sheets obtained in Examples 4 to 6 were slightly inferior in scratch resistance, thermal adhesion, embrittlement resistance with time, and embossing properties, but also excellent in transparency, whitening resistance over time, chemical resistance, and moldability. It was. The sheets obtained in Examples 1 to 6 were excellent in practicality as a building material sheet and an interior sheet.

  On the other hand, although the sheet obtained in Comparative Example 1 is excellent in transparency, the glass transition temperature TgA of the protective layer of layer A exceeds 70 ° C. and the crystallization parameter ΔTcA exceeds 60 ° C. , Whitening resistance over time, scratch resistance, chemical resistance, embossing properties are inferior, and the glass transition temperature TgB of the adhesive layer of the B layer exceeds 20 ° C. and the melting point TmB exceeds 210 ° C. The adhesiveness was inferior. Although the sheet obtained in Comparative Example 2 has excellent transparency, chemical resistance, and embossability, the glass transition temperature TgB of the adhesive layer of the B layer exceeds 20 ° C., and the melting point TmB exceeds 210 ° C. The embrittlement and thermal adhesiveness were inferior. The sheet obtained in Comparative Example 3 is excellent in scratch resistance, chemical resistance, and embossing property, but has a slightly small crystallization parameter ΔTcg of the protective layer of the A layer, so that it is easily crystallized, and has transparency and whitening resistance over time. The glass transition temperature and melting point of the B layer adhesive layer were slightly higher, and the resistance to embrittlement with time and thermal adhesiveness were somewhat inferior. Furthermore, although the sheet obtained in Comparative Example 4 is excellent in scratch resistance and chemical resistance, since the glass transition temperature of the protective layer of the A layer is less than 40 ° C., the embossability is inferior, and the glass of the adhesive layer of the B layer Since the transition temperature and the melting point were slightly high, they were slightly inferior in resistance to embrittlement with time and thermal adhesion. The sheets obtained in Comparative Examples 1 to 4 were inferior in practicality as building material sheets and interior sheets.

  The sheet obtained in the present invention is used as an industrial material, packaging material, etc. that require transparency, scratch resistance, moldability, chemical resistance, and thermal adhesiveness, particularly preferably as a building material or interior sheet. it can.

Claims (6)

A laminated polyester sheet having a two-layer configuration of at least A / B, wherein the A layer is a protective sheet layer, the B layer is an adhesive layer, and satisfies the following (1) to (2).
(1) The protective sheet layer of layer A is a polyester having a glass transition temperature TgA in the range of 40 to 70 ° C and a crystallinity parameter ΔTcg in the range of 30 to 60 ° C.
(2) The adhesive layer of the B layer is a polyester having a glass transition temperature TgB in the range of -20 to 20 ° C and a melting point TmB in the range of 120 to 210 ° C. The laminated polyester sheet according to claim 1, wherein the polyester of the A layer satisfies the following (A) and (B).
(A) It is comprised from the polyester which consists of a monomer composition which contains 90 mol% or more of aromatic dicarboxylic acid components with respect to all the dicarboxylic acid components.
(B) A monomer containing ethylene glycol as an essential component and 90 mol% or more of a glycol component consisting of at least one selected from 1,3-propanediol and 1,4-butanediol with respect to all glycol components Consists of polyester made of composition. The laminated polyester sheet according to claim 1, wherein the polyester of the B layer satisfies the following (a) and (b).
(A) It is composed of a polyester having a monomer composition containing aromatic dicarboxylic acid in the range of 60 to 90 mol% and aliphatic dicarboxylic acid in the range of 10 to 40 mol% with respect to all dicarboxylic acid components. That.
(B) With respect to all glycol components, ethylene glycol is in the range of 20 to 80 mol%, and at least one selected from 1,3-propanediol and 1,4-butanediol is 80 to 20 mol%. It is comprised from the polyester which consists of a monomer composition contained in the range.   The laminated polyester sheet according to claim 3, wherein a dimer content in the aliphatic dicarboxylic acid component is 70 to 90% by weight, and a trimer content is 10 to 30% by weight.   The laminated polyester sheet according to claim 3 or 4, wherein the aliphatic dicarboxylic acid component is a dimer acid or a dimer acid derivative.   A decorative sheet, wherein the laminated polyester sheet is laminated on the interior base material so that the layer A of the laminated polyester sheet according to any one of claims 1 to 5 becomes an outer surface.