JP2008143024A - Matted laminated polyester film and wall paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a matted laminated polyester film which is excellent in contamination resistance, chemical resistance, moldability, thermal adhesiveness, matting property, embossing property, and steam barrier property or the like, and especially suitable for application for wall paper. <P>SOLUTION: The laminated polyester film includes at least two layers of an A-layer and a B-layer. In the matted laminated polyester film, the A-layer is composed of a composition of 20-98 pts.wt. of a polyester (a) and 2-40 pts.wt. of an aliphatic dicarboxylic acid copolyester (b), the polyester has a glass transition temperature TgA of 30-70°C, the B-layer is the copolyester having a melting point TmB of 120-210°C, a crystal melting heat amount ΔHmB of 5-30 J/g, and a surface glossiness of the A-layer surface positioned at the uppermost surface is less than 50%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an improvement of a conventional flexible film. More specifically, the present invention is excellent in stain resistance, chemical resistance, moldability, thermal adhesiveness, matteness, embossing, gas barrier properties, particularly water vapor barrier properties. The matted laminated polyester film and this matted laminated polyester film are compatible with stain resistance, chemical resistance, embossing, matting after embossing, and thermal adhesion to the substrate. The present invention relates to a wallpaper that is capable of being easily handled without causing embrittlement over time.

  A typical flexible film is a polyvinyl chloride film. This polyvinyl chloride film is preferably used because it is excellent in weather resistance and is suitable not only for various processing such as embossing, but also at low cost. However, polyvinyl chloride film has problems such as the generation of toxic gas when the film burns due to fire and the like, and the problem of bleeding out of plasticizer. It has been demanded. One application development of flexible films is a wallpaper surface layer film. The purpose of this application is to coat the surface of polyvinyl chloride resin wallpaper or decorative plate (hereinafter referred to as PVC wallpaper) or polyvinyl chloride leather. The required properties of the film include prevention of plasticizer bleeding. Various properties such as heat resistance, chemical resistance, processability such as embossing, and thermal adhesion to a PVC base material are required.

  At present, ethylene / vinyl alcohol copolymer (hereinafter referred to as EVOH) film is mainly used as a wallpaper surface layer film, and this EVOH film has plasticizer bleeding prevention and chemical resistance among the above required characteristics. Although it has good workability such as embossing and embossing (see, for example, Patent Document 1), it has been necessary to coat an adhesive layer (for example, see Patent Document 2) because thermal adhesiveness to PVC wallpaper is not good. .

  Also, for interior decorations such as wallpaper, matte ones are preferred over high-gloss ones, and matte is also common for PVC wallpaper.

  Known methods for matting include sandblasting and surface treatment with chemicals, but these methods have the disadvantage of increasing costs. In addition, as another matting method, for example, a method of adding inorganic particles (for example, see Patent Document 3) has been proposed, but satisfactorily matte could not be performed by these methods. .

  Further, as a method of matting, a method of adding a thermoplastic resin (for example, see Patent Document 4) has been proposed. Although this method is difficult to return to matte when heated, such as embossing, and excellent in matte properties, the film whose base resin is EVOH is excellent in stain resistance such as crayon, coffee, aqueous pen, soy sauce, etc. Adhesives attached to the surface of EVOH film during curry and wallpaper joints and construction are difficult to wipe off and cause yellowing over time, resulting in poor stain resistance, chemical resistance to kitchen bleach, household detergents, etc. However, the glass transition temperature is slightly high, and the embossability is poor. Moreover, the film whose base resin is EVOH is excellent in gas barrier property. However, the oxygen barrier property is excellent, but the water vapor barrier property is significantly inferior, so moisture easily passes through the film.After the wallpaper is applied, the moisture content of the adhesive moves to the film surface over time, or on the film surface. There was a problem that mold was easily generated when moisture adhered.

Furthermore, a laminated film in which a highly crystalline polyester is laminated on one side of a flexible film (see, for example, Patent Document 5) has been proposed. This laminated film is excellent in flexibility and transparency, but is matte. The present condition is that the film which has property is not achieved.
JP 60-224542 A JP 60-239233 A Japanese Patent No. 3172559 Japanese Patent No. 3474276 JP-A-5-131601

  As described above, there has been a strong demand for a film for a wallpaper surface layer, particularly wallpaper, which has functions of stain resistance, chemical resistance, embossing and thermal adhesiveness, and is particularly difficult to deluster when heated. Further, there is a need for a wallpaper surface layer film that blocks gas barrier properties, particularly water vapor permeability.

  The present invention has been achieved as a result of investigations for solving the problems of the prior art as described above. The barrier property of plasticizers for polyvinyl chloride resin, stain resistance, chemical resistance, moldability, Matte laminated polyester film that is excellent in thermal adhesiveness, matteness, embossing, gas barrier property, especially water vapor barrier property, and does not easily return to matte when heated, and using this matted laminate polyester film, stain resistance, The aim is to provide a wallpaper that is compatible with chemical resistance, embossing, matte after embossing, and thermal adhesiveness to the substrate, and that is easy to handle without causing embrittlement over time. Is.

  As a result of intensive studies to achieve the above object, the present inventors made the film a laminated structure, and by setting the polyester composition, crystallinity or thermal characteristics of each layer, and the surface glossiness of the A layer surface within a specific range, The present inventors have found that an effect corresponding to the above object can be obtained, and have reached the present invention.

  That is, in order to achieve the above object, according to the present invention, a laminated polyester film having at least two layers of an A layer and a B layer, wherein the A layer comprises 20 to 98 parts by weight of polyester (a), fat A polyester having a glass transition temperature TgA of 30 to 70 ° C., and the B layer has a melting point TmB of 120 to 210 ° C. and a heat of crystal melting. A matted laminated polyester film is provided, which is a copolyester having a ΔHmB of 5 to 30 J / g, and the surface glossiness of the layer A surface located on the outermost surface is less than 50%.

In the matted laminated polyester film of the present invention,
(A) The thermoplastic resin (c) and / or inorganic filler (d) is added to 100 parts by weight of the polyester (a) and the aliphatic dicarboxylic acid copolymerized polyester (b) in the polyester of the A layer. Containing up to parts by weight,
(B) the aliphatic dicarboxylic acid copolymer polyester (b) of the A layer has a long-chain aliphatic dicarboxylic acid component;
(C) The copolymer polyester constituting the B layer satisfies the following (1) and (2). (1) For all dicarboxylic acid components, the aromatic dicarboxylic acid component is 60 to 99 mol% and long chain Containing 1 to 40 mol% of an aliphatic dicarboxylic acid component,
(2) The glycol component contains at least one glycol component having less than 10 carbon atoms,
(D) The long-chain aliphatic dicarboxylic acid component in the aliphatic dicarboxylic acid copolyester (b) of the A layer and / or the copolyester constituting the B layer has a dimer dicarboxylic acid content of 70. -90 wt%, and the content of trimer dicarboxylic acid is 10-30 wt%,
(E) the long-chain aliphatic dicarboxylic acid component is a dimer acid or a dimer acid derivative;
Are mentioned as preferable conditions.

  The wallpaper of the present invention is characterized in that the matted laminated polyester film and the wallpaper substrate are laminated so that the layer A of the matted laminated polyester film is an outer surface, and in particular, the wallpaper substrate. Preferably includes a polyolefin resin layer or a polyvinyl chloride resin layer.

  According to the present invention, as described below, the barrier of plasticizer for polyvinyl chloride resin, stain resistance, chemical resistance, moldability, thermal adhesiveness, matteness, embossing, gas barrier properties, especially A matted laminated polyester film that is excellent in water vapor barrier properties and difficult to return to matte when heated can be obtained.

  The matted laminated polyester film obtained by the present invention is useful as various industrial materials and packaging materials by taking advantage of the above-mentioned excellent characteristics, but is particularly suitable for wallpaper applications. , Chemical resistance, embossing, matte after embossing and thermal adhesiveness with the substrate are possible, and it is possible to obtain a wallpaper with excellent handling without causing embrittlement over time . In particular, since the matted laminated polyester film obtained in the present invention is excellent in thermal adhesiveness with a wallpaper substrate having a high expansion ratio, it is advantageous in obtaining a wallpaper adhered to the high expansion ratio wallpaper substrate.

  Hereinafter, preferred embodiments of the matted laminated polyester film and wallpaper according to the present invention will be described.

  The matted laminated polyester film of the present invention is a laminated polyester film having at least two layers of an A layer and a B layer, and the A layer comprises 20 to 98 parts by weight of polyester (a) and an aliphatic dicarboxylic acid copolyester. (B) A polyester having a composition of 2 to 40 parts by weight and having a glass transition temperature TgA of 30 to 70 ° C, and the B layer has a melting point TmB of 120 to 210 ° C and a crystal melting heat ΔHmB of 5 to 30 J /. The surface glossiness of the surface of the layer A located on the outermost surface is less than 50%.

  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.

  On the other hand, the A layer of the matted laminated polyester film of the present invention is a layer having chemical resistance by using the polyester (a) as a crystalline polyester.

  The A layer is a layer having formability represented by embossing or the like. Molding such as embossing is usually heated for a certain period of time above the glass transition temperature (hereinafter abbreviated as Tg) of the polymer, formed into a required shape, and then cooled to a temperature below Tg. Therefore, the glass transition temperature of the A layer (hereinafter, the glass transition temperature of the A layer is abbreviated as TgA) is preferably 30 to 70 ° C, more preferably 35 to 65 ° C, and still more preferably 40 to 40 ° C. 60 ° C.

  If TgA exceeds 70 ° C, embossing may be difficult to be applied. If TgA is less than 30 ° C, the room temperature becomes Tg or higher. This is not preferable because the deformation may proceed.

  From the viewpoint of having crystallinity, the polyester (a) constituting the A layer is preferably a crystalline polyester having a crystallization parameter ΔTcg of less than 60 ° C. Here, ΔTcg is the difference (Tc−Tg) between the crystallization temperature (Tc) and the glass transition temperature (Tg) measured in the temperature rising process of differential scanning calorimetry (DSC). Crystalline polyester can produce microcrystals having a visible light size or less in the cooling process by controlling the thickness after melt extrusion and the cooling temperature.

  Typical polymers of crystalline polyesters having a ΔTcg of less than 60 ° C. include polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene adipate, polyethylene sebacate, polybutylene adipate, polybutylene sebacate, polybutylene naphthalate, and their It is represented by a derivative such as a copolymer. In view of further having crystallinity, ΔTcg is preferably less than 50 ° C., and particularly preferably less than 40 ° C.

  The polyester (a) constituting the A layer in the matted laminated polyester film of the present invention is a general term for high molecular weight bodies constituted by ester bonds.

  Examples of the dicarboxylic acid component used for the ester bond of the polyester (a) include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodium sulfoisophthalic acid. , Aromatic dicarboxylic acids such as phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, cyclohexyne dicarboxylic acid and other alicyclic dicarboxylic acids, p -Oxycarboxylic acids such as oxybenzoic acid can be used.

  Among these, in the polyester (a) used for the matted laminated polyester film of the present invention, the proportion of terephthalic acid and / or naphthalenedicarboxylic acid as the dicarboxylic acid component is preferably 80 mol% or more, more preferably 85 mol%. From the viewpoints of control of ΔTcg and Tg, productivity, and cost, particularly preferably 95 mol% or more.

  On the other hand, examples of the glycol component of the polyester (a) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, , 4-butanediol, 1,2-butanediol, 1,5-pentylglycol, 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, 1,3-cyclo Examples include pentane dimethanol and 1,4-cyclohexane dimethanol.

  Among these, in the polyester (a) used for the matted laminated polyester of the present invention, the proportion of one or more glycol components selected from the group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol is In view of control of ΔTcg and Tg, productivity, and cost, it is preferably 80 mol% or more.

  These dicarboxylic acid components and glycol components may be used in combination of two or more. Of these, the glycol component is particularly preferably ethylene glycol or / and 1,4-butanediol.

  In the matted laminated polyester film of the present invention, the aliphatic dicarboxylic acid copolymerized polyester (b) constituting the A layer has fine irregularities formed on the surface of the polyester (a). However, it is not particularly limited as long as the matte property is improved.

  In particular, the aliphatic dicarboxylic acid copolyester (b) is preferably a long chain aliphatic dicarboxylic acid copolyester because it is particularly excellent in matting.

  The copolymer polyester constituting the layer B of the matted laminated polyester film of the present invention is particularly a copolymer polyester having a melting point TmB of 120 ° C. to 210 ° C. and a crystal melting heat ΔHmB of 5 to 30 J / g. Although not limited, it is particularly preferably a long-chain aliphatic dicarboxylic acid copolyester.

  The aliphatic dicarboxylic acid copolyester (b) in the A layer of the matted laminated polyester film of the present invention and the long chain aliphatic dicarboxylic acid copolyester suitably used in the copolyester constituting the B layer are: As a dicarboxylic acid component, a hard segment having an aromatic dicarboxylic acid component as a main component, a soft segment having a long-chain fatty acid dicarboxylic acid component as a main component, and a glycol component having less than 10 carbon atoms as a glycol component It is preferable that at least one kind is contained.

  The aromatic dicarboxylic acid component constituting the hard segment of the long-chain aliphatic dicarboxylic acid copolymerized polyester preferably used for the aliphatic dicarboxylic acid copolymerized polyester (b) and the copolymerized polyester constituting the B layer is an aromatic dicarboxylic acid And its ester-forming derivatives. Specific examples of such aromatic dicarboxylic acids include, for example, isophthalic acid, terephthalic acid, diphenyl-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalene 2,7-dicarboxylic acid, naphthalene 1, Examples include 5-dicarboxylic acid, diphenoxyethane 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 in the long-chain aliphatic dicarboxylic acid copolymerized polyester suitably used for the aliphatic dicarboxylic acid copolymerized polyester (b) and the copolymerized polyester constituting the B layer is 60% of the total dicarboxylic acid component. It is preferable that it is -99 mol%. More preferably, it is 60-97 mol%, Most preferably, it is 70-95 mol%. When the amount of the aromatic dicarboxylic acid component is less than 60 mol%, the crystallinity is deteriorated and the chemical resistance may be deteriorated. If the amount of the aromatic dicarboxylic acid component exceeds 99 mol%, flexibility may not be obtained.

  In the long-chain aliphatic dicarboxylic acid copolymer polyester suitably used for the aliphatic dicarboxylic acid copolymer polyester (b) and the copolymer polyester constituting the B layer, the long-chain aliphatic dicarboxylic acid component constituting the soft segment is as follows: Those derived from unsaturated fatty acids having 10 or more carbon atoms represented by the formula are preferred, and derivatives derived from unsaturated fatty acids having 10 to 30 carbon atoms are particularly preferred. It is obtained mainly from a dimerized fatty acid (hereinafter abbreviated as a dimer) obtained by dimerization of an unsaturated fatty acid or an ester-forming derivative of the dimer.

_{CH 3 (CH 2) m (} CH = CH-CH 2) k (CH 2) n COOR
(In the formula, R is a hydrogen atom or an alkyl group, m is an integer of 1 to 25, k is an integer of 1 to 5, n is an integer of 0 to 25, and m, k, and n are 8 ≦ m + 3k + n ≦ 28. Satisfies the relational expression.)
In the dimerization reaction of the unsaturated fatty acid, a trimerized fatty acid (hereinafter abbreviated as trimer) obtained by trimerization of the unsaturated fatty acid is also generated together with the dimer. Therefore, the long-chain aliphatic dicarboxylic acid derivative obtained by the dimerization reaction of the unsaturated fatty acid contains a dimer, a trimerized trimer, and an unreacted monomer.

  When this long-chain fatty acid dicarboxylic acid derivative is purified by a plurality of distillations, etc., and a high-purity long-chain aliphatic dicarboxylic acid derivative having a dimer amount of 95% or more, more preferably 98% or more is used, in terms of color tone A good copolyester is obtained. However, since the cost of the long-chain aliphatic dicarboxylic acid derivative is remarkably increased by the distillation process, in order to achieve both the color tone and cost performance of the aliphatic dicarboxylic acid copolymer polyester, It is preferable that the ratio of a trimer and a trimer is 70 to 90 weight% and 10 to 30 weight%, respectively. That is, in the long-chain aliphatic dicarboxylic acid copolyester used for the aliphatic dicarboxylic acid copolyester (b) constituting the A layer and the copolyester constituting the B layer, The dimer content is preferably 70 to 90% by weight and the trimer content is preferably 10 to 30% by weight.

  Moreover, the long-chain aliphatic dicarboxylic acid used at the time of manufacture of the long-chain aliphatic dicarboxylic acid copolymerized polyester used for the copolymerized polyester such as the aliphatic dicarboxylic acid copolymerized polyester (b) and the B layer constituting the A layer The derivative has an unsaturated bond generated by dimerization reaction of unsaturated fatty acid, but it may be used as it is as a raw material for polymerization or after reduction by hydrogenation reaction. However, particularly when heat resistance, weather resistance and transparency are required, it is preferable to use a dimer in which unsaturated bonds are eliminated by hydrogenation.

  It is a long-chain aliphatic dicarboxylic acid derivative that can be used in the production of a long-chain aliphatic dicarboxylic acid copolymerized polyester used in a copolymerized polyester such as the aliphatic dicarboxylic acid copolymerized polyester (b) and B layer constituting the A layer. As the dimer of the unsaturated fatty acid, a dimer acid having 36 carbon atoms and a dimer acid derivative obtained by esterifying the dimer acid 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” from Unikema International, or various esters thereof. Forming derivatives are commercially available. One or more of the above compounds may be used in combination.

  In the long-chain aliphatic dicarboxylic acid copolymer polyester suitably used for the aliphatic dicarboxylic acid copolymerized polyester (b) constituting the A layer of the present invention, the amount of the long-chain aliphatic dicarboxylic acid component constitutes the A layer. 1-40 mol% in all the dicarboxylic acid components in the long-chain aliphatic dicarboxylic acid copolymerized polyester of the aliphatic dicarboxylic acid copolymerized polyester (b) is preferable, more preferably 3-35%, still more preferably 5-5%. 30 mol%.

  The amount of the long-chain aliphatic dicarboxylic acid component in the long-chain aliphatic dicarboxylic acid copolymerized polyester suitably used for the aliphatic dicarboxylic acid copolymerized polyester (b) When it exceeds 40 mol% in an acid component, the heat resistance of polyester may fall and the mechanical characteristics of the molded product obtained from this may fall.

  On the other hand, the amount of the long-chain aliphatic dicarboxylic acid component in the long-chain aliphatic dicarboxylic acid copolymerized polyester suitably used for the aliphatic dicarboxylic acid copolymerized polyester (b) is the same as that of the long-chain aliphatic dicarboxylic acid copolymerized polyester. When it is less than 1 mol% in the total dicarboxylic acid component, it becomes easy to be compatible with the polyester (a), and the matte property may be inferior.

  Here, the polyester (a) constituting the A layer of the present invention may be copolymerized with the above long-chain fatty acid dicarboxylic acid component as long as the crystallinity is not impaired, or a resin composed of other components. You may mix.

  When the aliphatic dicarboxylic acid copolyester (b) of layer A of the present invention is a long-chain aliphatic dicarboxylic acid copolyester, it contains at least one glycol component having 10 or less carbon atoms as the glycol component. Preferably it is.

  Specific examples of the glycol component having less than 10 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, and 1,3-butanediol. 1,4-butanediol, 1,2-butanediol, 1,5-pentylglycol, 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, 1,3 -Cyclopentanedimethanol, 1,4-cyclohexanedimethanol, etc. are mentioned.

  Among these, at least one selected from ethylene glycol, 1,3-propanediol, and 1,4-butanediol is preferable. 1,4-butanediol is an essential component, and ethylene glycol and 1,3 -More preferably, one or more of the propanediols are selected. The reason why it is preferable to select a multi-component glycol is that when there is only one glycol component, it is difficult to control the crystallinity, and the crystallinity is obtained by copolymerizing a plurality of glycol components and changing the blending amount. It is because it becomes possible to control.

  The B layer of the present invention preferably has a melting point of 120 to 210 ° C. and a heat of crystal fusion of 5 to 30 J / g. That is, the copolymer polyester constituting the B layer has a melting point TmB (here, the melting point of the copolymer polyester constituting the B layer is abbreviated as TmB) of 120 to 210 ° C., and a crystal melting heat ΔHmB (here, The copolyester constituting the layer B is preferably a copolyester having a heat of crystal melting of 5-30 J / g (abbreviated as ΔHmB), and the others are not particularly limited, but the handling property, TmB control, ΔHmB A long-chain aliphatic dicarboxylic acid copolyester is more preferable from the viewpoint of control, film-forming property, and productivity.

  Further, when the aliphatic dicarboxylic acid copolymerized polyester (b) constituting the A layer is a long-chain aliphatic dicarboxylic acid copolymerized polyester, the copolymerized polyester constituting the B layer is from the viewpoint of film forming property and productivity. It is preferable to use the same long-chain aliphatic dicarboxylic acid copolyester as the aliphatic dicarboxylic acid copolyester (b).

  The copolyester constituting the B layer is preferably a long-chain aliphatic dicarboxylic acid copolyester as described above, but the aromatic dicarboxylic acid component is used as the total dicarboxylic acid component of the copolyester constituting the B layer. And a monomer composition containing 90 mol% or more of an ethylene glycol component and 1,4-butanediol component as a total glycol component of the copolyester constituting the B layer, and containing 90 mol% or more of a long-chain aliphatic dicarboxylic acid component It is preferable that the polyester is a copolymerized polyester. More preferably, the total dicarboxylic acid component of the copolyester constituting the B layer is 95 mol% or more of the aromatic dicarboxylic acid component and the long-chain aliphatic dicarboxylic acid component, and the total glycol of the copolyester constituting the B layer. As components, the ethylene glycol component and the 1,4-butanediol component are 95 mol% or more. The long-chain aliphatic dicarboxylic acid copolymer polyester of the copolyester constituting the B layer is composed of 90% aromatic dicarboxylic acid component and long-chain aliphatic dicarboxylic acid component as the total dicarboxylic acid component of the copolyester constituting the B layer. When it is less than mol%, or when it consists of a monomer composition in which the ethylene glycol component and the 1,4-butanediol component are less than 90 mol% as the total glycol component, handleability, control of melting point, film-forming property, production Since it may be inferior in the point of property, it is not preferable.

  More preferably, the copolymer polyester constituting the B layer is a long-chain aliphatic dicarboxylic acid copolymer polyester, and the aromatic dicarboxylic acid component is added to the total dicarboxylic acid component of the copolymer polyester constituting the B layer. This is a case of 60 to 99 mol% and a copolyester containing 1 to 40 mol% of a long-chain aliphatic dicarboxylic acid component. When the aromatic dicarboxylic acid component is less than 60 mol% or the long-chain aliphatic dicarboxylic acid component exceeds 40 mol% with respect to the total dicarboxylic acid component of the copolyester constituting the B layer, the handling property, melting point It is not preferable in terms of control, film forming property, and productivity. Conversely, when the aromatic dicarboxylic acid component exceeds 99 mol% or the long-chain aliphatic dicarboxylic acid component is less than 1 mol%, the glass transition temperature and the melting point TmB become too high, and the wallpaper base material such as polyvinyl chloride It is not preferable because it may be inferior in the thermal adhesiveness.

  More preferably, the aromatic dicarboxylic acid component is 70 to 95 mol% and the long-chain aliphatic dicarboxylic acid component is 5 to 30 mol% with respect to the total dicarboxylic acid component of the copolyester constituting the B layer.

  The long-chain aliphatic dicarboxylic acid copolyester preferably used for the copolyester constituting the B layer preferably contains at least one glycol component having a carbon number of less than 10 as a glycol component. More preferably, the glycol component of the long-chain aliphatic dicarboxylic acid copolymer polyester preferably used for the copolymer polyester constituting the B layer preferably contains at least one glycol component having less than 10 carbon atoms.

  Here, the glycol component having less than 10 carbon atoms can be arbitrarily set. However, the polyester of the B layer is preferably a copolymer polyester having a melting point TmB of 120 ° C. to 210 ° C. When designing a copolymer polyester satisfying the melting point TmB of 120 to 210 ° C., The glycol component having less than 10 carbon atoms is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, particularly preferably 70 to 100 mol% based on the total glycol component of the copolymerized polyester. 100 mol%.

  On the other hand, the amount of the other glycol component is preferably from 0 to less than 50 mol%, more preferably from 0 to 40 mol%, particularly preferably from 0 to 0 mol%, based on the total glycol components of the copolymer polyester constituting the B layer. 30 mol%.

  The melting point TmB of the copolyester constituting the B layer is preferably 120 ° C. to 210 ° C. from the viewpoint of achieving both film-forming properties and thermal adhesion to a wallpaper substrate such as polyvinyl chloride. When the TmB exceeds 210 ° C., the thermal adhesiveness may be deteriorated, which is not preferable. Moreover, when TmB is less than 120 ° C., the film forming property may be deteriorated, which is not preferable.

  Further, the heat of crystal fusion ΔHmB of the copolyester constituting the layer B of the present invention is 5 to 30 J / g from the viewpoint of film-forming properties and thermal adhesiveness to a base material for wallpaper such as polyvinyl chloride. preferable. For wallpaper base materials such as polyvinyl chloride, in order to impart design properties, a cushioning foam is generally used which is foamed by adding a foaming agent to the base resin for wallpaper together with embossing. . A foam that is particularly widely used as a base material for wallpaper is a polyvinyl chloride foam foamed to 2 to 5 times its original thickness.

  A wallpaper base material having a foaming ratio of less than 4 times (hereinafter abbreviated as a low foaming wallpaper base material) and a wallpaper base material having a foaming ratio of 4 times or more (hereinafter abbreviated as a high foaming wallpaper base material) are bonded to a wallpaper film. In some cases, the manufacturing method for the bonding is different.

  For example, the low-foaming wallpaper base material is foamed at 230 to 240 ° C., and then embossed with an embossing roll, and at the same time, it is bonded to the wallpaper film by preheating.

  On the other hand, the highly foamed wallpaper base material is foamed at 230 to 240 ° C. and then once cooled to room temperature to 50 ° C. in order to maintain the foamed shape. After cooling, the wallpaper substrate is heated with a radiation heater or the like, and is bonded to the wallpaper film at the same time as embossing. However, the high-foaming wallpaper substrate is not subject to the same embossing roll pressure and temperature as the low-foaming wallpaper substrate, and is usually less than one third of the low-foaming wallpaper substrate pressure. Adhesiveness with wallpaper film may be inferior. That is, the thermal adhesiveness with the highly foamed wallpaper base material may be inferior in thermal adhesiveness only by setting TmB in the range of 120 to 210 ° C.

  When this point was examined, it was found that the thermal adhesiveness with the highly foamed wallpaper base material is improved by setting the crystal melting heat ΔHmB to 5 to 30 J / g. That is, the heat of crystal fusion of the B layer is preferably 5 to 30 J / g, and more preferably the heat of crystal fusion is 5 to 25 J / g. Therefore, ΔHmB of the copolyester constituting the B layer is preferably 5 to 30 J / g, more preferably ΔHmB is 5 to 25 J / g.

  When ΔHmB exceeds 30 J / g, the thermal adhesiveness with the highly foamed wallpaper base material may be inferior, which is not preferable. On the other hand, if it is less than 5 J / g, the polymer tends to be amorphous and the film-forming property tends to be inferior.

  In order to make ΔHmB of the copolyester constituting the B layer within the above range, the total dicarboxylic acid component of the copolyester constituting the B layer is 60 to 99 mol% of aromatic dicarboxylic acid, long-chain aliphatic dicarboxylic acid. It is preferable to make an acid component into 1-40 mol%. Moreover, as an aromatic dicarboxylic acid component used for the copolyester constituting the B layer, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and ester-forming derivatives thereof are preferable. Further, these aromatic dicarboxylic acid components are preferably used in combination of two kinds from the viewpoint of easy control of TmB and ΔHmB. More preferably, it is a case where the long-chain aliphatic dicarboxylic acid component is a dimer acid derivative obtained by esterifying the above-mentioned dimer acid and dimer acid because TmB and ΔHmB can be easily controlled.

  On the other hand, the glycol component of the copolyester constituting the B layer preferably contains at least one glycol component having less than 10 carbon atoms. More preferably, in order to make ΔHmB within the above range, the glycol component having less than 10 carbon atoms is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%. The amount of the other glycol component is preferably less than 50 mol% with respect to the total glycol component of the copolyester constituting the layer B. To make ΔHmB in the above range, it is more preferably 0 to 40 mol%. Especially preferably, it is 0-30 mol%.

  Particularly preferably, the TmB is set to 120 ° C. to 210 ° C. and the ΔHmB is set to 5 to 30 J / g. As the acid component, terephthalic acid is preferably 50 to 90 mol%, isophthalic acid or adipic acid or 5-sodium sulfoisophthalic acid is 5 to 25 mol%, and dimer acid is 5 to 25 mol%. As a glycol component, 1, 4- butanediol 50-100 mol% and ethylene glycol 50-0 mol% are preferable.

  The function of the B layer of the present invention includes adhesion to a wallpaper substrate and the like, and another function is to suppress the embrittlement of the film over time.

  In general, an unstretched film of polyester is rapidly cooled below the glass transition temperature to become amorphous. Amorphized films are thermodynamically non-equilibrium in the glassy state, and at temperatures near the glass transition temperature, thermodynamic quantities such as volume and enthalpy relax, and physical modification without chemical changes ( physical aging) occurs. Due to the volume relaxation or enthalpy relaxation, a non-uniform structure occurs in the film, and the non-uniform structure tends to be a defect and the film tends to be brittle.

  On the other hand, since the biaxially stretched film is crystallized or oriented, the molecules do not move easily, and this embrittlement phenomenon hardly occurs. This embrittlement phenomenon is a crystallizable polymer having a glass transition temperature near room temperature, and is caused by forming an amorphous film. The embrittlement is delayed as the thickness of the film increases and the intrinsic viscosity (IV) of the film increases. This specific example can be confirmed by measuring a tensile test.

  For example, when a single layer film (film thickness 20 μm) of the A layer of the present invention is produced, the breaking elongation of the film immediately after production has several hundred%, but the breaking elongation after aging (one week) is several%. It turns out that it becomes. When this embrittlement phenomenon occurs, film tearing may occur in post-processing steps such as film bonding and slitting, resulting in poor handling. In the present invention, it is possible to suppress the embrittlement with time by laminating the B layer having a glass transition temperature of room temperature or lower on the A layer.

  In the long-chain aliphatic dicarboxylic acid copolyester preferably used for the copolyester constituting the B layer of the present invention, in addition to the above components, other components are copolymerized within a range not impairing the object of the present invention. Alternatively, a resin composed of other components may be mixed. For example, as copolymerizable dicarboxylic acid components, 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, and examples of the hydroxycarboxylic acid component include p-oxybenzoic acid, p-hydroxymethylbenzoic acid, or ester derivatives thereof. In addition, as a glycol component, 1,12-dodecanediol, diethylene glycol, polyoxyalkylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, spiroglycol, or bisphenol A, bisphenol S and These ethylene oxide adducts, trimethylolpropane and the like can be mentioned.

  The melt viscosity of the resin used in the A layer and the B layer of the present invention 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 film or the like, the extruded state is not stable, and the polyester may have a non-uniform film thickness. 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.

  In order to set the melt viscosity of the A layer and the B layer of the present invention in the range of 1000 to 3000 poise at 250 ° C., the polyester (a) constituting the A layer of the present invention, the aliphatic dicarboxylic acid copolyester (b) The intrinsic viscosity of a polyester such as a copolyester constituting the B layer is preferably in the range of 0.5 to 1.2. When the intrinsic viscosity of the polyester such as polyester (a) constituting the A layer of the present invention, aliphatic dicarboxylic acid copolymerized polyester (b) or copolymerized polyester constituting the B layer exceeds 1.2, the polyester becomes a film or the like. In the case of extrusion molding, the extruded state is not stable, and a non-uniform film thickness may be given. Furthermore, the partially thickened portion may be whitened and spotted. In addition, when the intrinsic viscosity is less than 0.5, the film formation may be difficult due to insufficient viscosity. The melt viscosity was measured at 250 ° C. using a melt index after the polyester pellets constituting the A layer and the B layer were vacuum dried at 150 ° C. for 5 hours or more.

  The above-described method for producing the long-chain aliphatic dicarboxylic acid copolymer 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 a long-chain aliphatic dicarboxylic acid derivative from a composition containing the specific range described above may be used, or two or more kinds of polymers and Alternatively, a method may be used in which the copolymer is 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, a long-chain aliphatic dicarboxylic acid derivative and a glycol component. And the like so that the above-mentioned specific polymerization composition is obtained. Cost advantage that general-purpose aromatic polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) can be used, and the components contained in the copolymer polyester only by changing the mixing amount of the aromatic polyester and copolymer The long-chain aliphatic dicarboxylic acid copolymer polyester of the present invention is prepared by melting and kneading an aromatic polyester and an aliphatic-aromatic polyester copolymer in an extruder from the viewpoint of handling properties that can be freely controlled. Among them, the constituent component is mainly “at least selected from the group consisting of a terephthalic acid component and / or an isophthalic acid component, an ethylene glycol component, a 1,3-propanediol component, and a 1,4-butanediol component. Aromatic polyester , A fat mainly composed of “a terephthalic acid component, a fatty acid or its derivative component, an ethylene glycol component, a 1,3-propanediol component, and a 1,4-butanediol component” A method in which an aromatic-aromatic copolymer polyester is melt-kneaded in an extruder to obtain the above-described specific polymerization composition is preferable, and the constituents are aromatics mainly composed of “terephthalic acid and / or isophthalic acid component and ethylene glycol component”. Specificity described above by melting and kneading polyester and an aliphatic-aromatic polyester copolymer mainly composed of “terephthalic acid, fatty acid or its derivative component, and 1,4-butanediol” in an extruder The method of making it a polymerization composition is more preferable.

  As the latter method, the copolymer polyester constituting the B layer is composed of an aromatic polyester composed of an aromatic dicarboxylic acid and a glycol component, an aromatic dicarboxylic acid, a long-chain aliphatic dicarboxylic acid derivative, and a glycol component. And a method of melting and kneading an aliphatic-aromatic polyester copolymer in an extruder to obtain the above-described specific polymerization composition. Cost advantage that general-purpose aromatic polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) can be used, and the components contained in the copolymer polyester only by changing the mixing amount of the aromatic polyester and copolymer From the viewpoint of handling properties that can be freely controlled, a method in which an aromatic polyester and an aliphatic-aromatic polyester copolymer are melt-kneaded in an extruder to obtain the above-described specific polymerization composition is preferable. Aromatic polyester comprising “terephthalic acid component and / or isophthalic acid component, ethylene glycol component, 1,3-propanediol component, and 1,4-butanediol component”, and constituent components Is mainly "terephthalic acid component and fat In the extruder, an aliphatic-aromatic copolymer polyester comprising an acid or a derivative thereof and at least one selected from the group consisting of an ethylene glycol component, a 1,3-propanediol component, and a 1,4-butanediol component The above-mentioned specific polymerization composition is preferably melt-kneaded with an aromatic polyester composed mainly of “terephthalic acid and / or isophthalic acid component and ethylene glycol component”, and the structural component is mainly “terephthalic acid”. And an aliphatic-aromatic polyester copolymer composed of “a fatty acid or a derivative thereof and 1,4-butanediol” are further preferably kneaded in an extruder to obtain the specific polymerization composition described above.

  In order to improve the melt viscosity of the copolyester such as the B layer obtained by copolymerization and the compatibility of the polyester resin molded product, the following compatibilizer is added at the time of copolymerization or resin mixing. It is preferable. 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 melt viscosity or compatibility by adding the above compounds is not always clear.

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

  The composition constituting the layer A of the matted laminated polyester film of the present invention comprises a polyester (a) and an aliphatic dicarboxylic acid copolymerized polyester (b), a thermoplastic resin (c) and / or an inorganic filler (d). Can be included.

  In the present invention, the thermoplastic resin (c) is preferably a polymer that is incompatible with the polyester (a) of the A layer. Because the polyester (a) and the thermoplastic resin (c) are incompatible with each other, the thermoplastic resin (c) forms fine irregularities on the surface of the polyester (a) to obtain a film having an excellent matting effect. Can do. Moreover, when using an inorganic filler (d), the case where a thermoplastic resin (c) and an inorganic filler (d) are used together is especially preferable.

  Examples of the thermoplastic resin (c) incompatible with the polyester (a) include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamides such as nylon 6, and alicyclic rings Examples thereof include polyolefins, polyarylate, polycarbonate, polyethersulfone, and polysulfone. These polymers may be a single polymer, a copolymer polymer, or two or more kinds of blend polymers. Of these, preferred thermoplastic resins are polyolefins, polyesters, polyamides, and copolymers thereof. Examples of the polyester copolymer include polyester copolymer that is incompatible with the polyester copolymer used. Examples of the dicarboxylic acid include terephthalic acid or / and dimer acid, dodecanedioic acid, and the glycol component includes a copolymerized polyester of ethylene glycol or / and butanediol.

  As the thermoplastic resin (c), polyolefin and polyamide are particularly preferable from the viewpoint of matteness. As the copolyester, dimer acid copolyester and dodecanedioic acid polyester are preferably used in that they have a matte property.

  In the present invention, the inorganic filler (d) includes calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, clay, kaolin, sericite, glass flake, mica, smectite, vermiculite and other clay minerals. Of these, talc, silica, and mica are preferable from the viewpoints of miscibility with polyester and film-forming properties of the matted film. These inorganic fillers may be used alone or in combination of two or more. These inorganic fillers can be used as they are, or those subjected to a surface treatment with a surfactant, a silane coupling agent or the like can be used as necessary. The average particle size of the inorganic filler is preferably less than 10 μm, more preferably less than 5 μm, and particularly preferably less than 4 μm. Although a lower limit is not specifically limited, From a point of cost, it is about 0.1 micrometer.

  The inorganic filler (d) is added to the layer A of the matted laminated polyester film by adding the inorganic filler (d) to the polyester (a), the aliphatic dicarboxylic acid copolymerized polyester (b), and the thermoplastic resin (c). And a method of preparing and mixing master pellets of high-concentration inorganic filler (d) of polyester (a) or aliphatic dicarboxylic acid copolymerized polyester (b) or thermoplastic resin (c). preferable. Further, a method of dispersing the inorganic filler (d) during the polymerization of the polyester (a) in the A layer or a method of dispersing the inorganic filler (d) during the polymerization of the aliphatic dicarboxylic acid copolymerized polyester (b) may be used.

  In the present invention, the inorganic filler (d) and the thermoplastic resin (c) can be used simultaneously.

  A layer consists of polyester (a) and aliphatic dicarboxylic acid copolyester (b), and the blending ratio of polyester (a) and aliphatic dicarboxylic acid copolyester (b) is 20 to 98 weight percent of polyester (a). Parts, aliphatic dicarboxylic acid copolyester (b) 2 to 40 parts by weight is preferred. When the amount of the aliphatic dicarboxylic acid copolymerized polyester (b) is less than 2 parts by weight, the matte property may be lowered, which is not preferable. When the amount of the aliphatic dicarboxylic acid copolymerized polyester (b) is more than 40 parts by weight Since the amount of the polyester (a) is decreased, the heat resistance may be lowered.

  Further, the thermoplastic resin (c) and / or the inorganic filler (d) is contained in an amount of 40 parts by weight or less with respect to a total of 100 parts by weight of the polyester (a) of the A layer and the aliphatic dicarboxylic acid copolymerized polyester (b). It is preferable. Including the thermoplastic resin (c) and / or the inorganic filler (d) in the polyester of the A layer is preferable because the matte property is improved. More preferably, it contains 30 parts by weight or less of the thermoplastic resin (c) and / or the inorganic filler (d).

  More preferably, the A layer comprises polyester (a) and aliphatic dicarboxylic acid copolymerized polyester (b) and / or thermoplastic resin (c) and / or inorganic filler (d), and polyester (a) and aliphatic The blending ratio of the dicarboxylic acid copolymerized polyester (b), the thermoplastic resin (c) and the inorganic filler (d) is 60 to 90 parts by weight of the polyester (a), 5 to 20 parts by weight of the aliphatic dicarboxylic acid copolymerized polyester (b). Parts, thermoplastic resin (c) and / or inorganic filler (d) 5 to 20 parts by weight.

  By adding the thermoplastic resin (c) to the polyester (a) and the aliphatic dicarboxylic acid copolymerized polyester (b), the matte is made more than when only the polyester (a) and the aliphatic dicarboxylic acid copolymerized polyester (b) is used. This is preferable because of improved properties. Further, an inorganic filler (d) is preferably further blended, because a matted laminated polyester film that does not easily return to matte upon heating such as high temperature embossing or heat sealing is preferable.

  More preferably, it comprises polyester (a) and aliphatic dicarboxylic acid copolymerized polyester (b) and / or thermoplastic resin (c) and / or inorganic filler (d), and polyester (a) and aliphatic dicarboxylic acid copolymerized polyester. The blending ratio of (b), thermoplastic resin (c) and inorganic filler (d) is 65 to 85 parts by weight of polyester (a), 10 to 20 parts by weight of aliphatic dicarboxylic acid copolymerized polyester (b), and thermoplastic resin. (C) and / or inorganic filler (d) is 5 to 15 parts by weight.

  The method for obtaining the blending ratio of the polyester (a) of layer A and the aliphatic dicarboxylic acid copolymerized polyester (b) and / or the thermoplastic resin (c) and / or the inorganic filler (d) from the film state is as follows. Is mentioned. For example, the layer A is separated by scraping from the film, and subsequently, using various analytical means such as chromatography such as gel permeation chromatography (GPC) and nuclear magnetic resonance measurement (NMR), The blending ratio can be confirmed. Subsequently, the aliphatic dicarboxylic acid copolymerized polyester (b) is separated by chromatography such as GPC, and various analytical means such as NMR are used, or various analytical means are used after hydrolysis, thereby aliphatic dicarboxylic acid copolymerization. The composition of the polyester (b) can be identified. Similarly, other components such as polyester (a) and the composition ratio of the B layer can be confirmed. An inorganic filler (d) can confirm a composition ratio by measuring a weight, after burning at 600-700 degreeC and ashing.

  In the present invention, in order to melt-knead the polyester (a) and the aliphatic dicarboxylic acid copolymerized polyester (b) and / or the thermoplastic resin (c) and / or the inorganic filler (d), a twin screw extruder, A method of molding after previously kneading using a lavender plastograph or the like, or a method of directly feeding to various molding machines and molding while kneading with a molding machine, once producing high concentration master pellets with an extruder, There is a method of performing melt extrusion molding using a resin diluted to about 1/30. In order to disperse the inorganic filler more uniformly, a dispersion aid such as a metal soap such as sodium stearate, magnesium stearate or zinc stearate, ethylene bisfatty acid amide or polyethylene wax may be added. Moreover, you may add antioxidant and a ultraviolet absorber. The order of kneading is not particularly limited, and polyester (a) and aliphatic dicarboxylic acid copolymerized polyester (b) and / or thermoplastic resin (c) and / or inorganic filler (d) may be kneaded simultaneously, The polyester (a) and the aliphatic dicarboxylic acid copolymerized polyester (b) may be kneaded first, and the thermoplastic resin (c) and / or the inorganic filler (d) may be kneaded there. The filler (d) and / or the thermoplastic resin (c) may be mixed first, and an aliphatic dicarboxylic acid copolymer polyester (b) such as a long-chain aliphatic dicarboxylic acid copolymer polyester may be kneaded therein. The chain aliphatic dicarboxylic acid copolyester (b), the inorganic filler (d) and / or the thermoplastic resin (c) are first kneaded and then mixed with May be kneaded the ester (a).

  In order to improve the melt viscosity of the copolymerized polyester obtained by copolymerization and the transparency of the polyester resin molded article, it is also 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.

  The improvement in transparency due to the addition of the compatibilizing agent of the present invention is not restricted by a specific mechanism or hypothesis, but can be explained by the following model, for example.

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

[Organic acid addition effect]
When an aromatic polyester and an aliphatic-aromatic polyester copolymer are melt-kneaded to produce a copolyester or a film or molded product thereof, an ester exchange reaction between different polymers due to the acid catalytic effect of an organic acid. Is promoted, the formation of the copolyester is promoted, and the transparency is improved by homogenizing the polymer chain.

  The addition amount in the case where the compatibilizing agent shown above is added to the copolyester may be any amount as long as the melt viscosity reaches the desired viscosity level and exhibits the desired transparency. 5% by weight is preferred. Moreover, generally the addition amount when adding a compatibilizing agent to the said copolyester is 0.1 to 5 weight%.

  The matted laminated polyester film of the present invention is a film obtained by adding various particles and additives to the above-described copolymerized polyester as necessary, and then forming a film by a usual method, for example, melt extrusion. It is produced by cooling and solidifying, and stretching or heat treatment as necessary.

  When this matted laminated polyester film causes blocking, it is preferable to add particles to the B layer of the matted laminated polyester film as long as the thermal adhesiveness of the effect of the present invention is not impaired. The particles to be added 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. Examples include inorganic particles, organic particles, crosslinked polymer particles, and internal particles generated in the polymerization system. be able to. Two or more kinds of these particles may be added. The addition amount of the particles in the matted laminated polyester film is preferably 0.01 to 10% by weight, more preferably 0.02 to 1, from the viewpoint of thermal adhesiveness with a wallpaper substrate or the like. % 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. If the number average particle diameter is in such a preferred range, film defects are less likely to occur, and it is difficult to cause deterioration of transparency, moldability, and the like.

  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, or 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.

  It is preferable to add an antibacterial agent to the matted laminated polyester film of the present invention in terms of imparting antibacterial properties. As the antibacterial agent, photocatalytic titanium oxide such as zeolite, glass, silica gel and the like containing metal ions such as silver, copper, zinc, aluminum and magnesium can be used. Among these, zeolite and glass containing metal ions of silver, copper and zinc are preferable from the viewpoint of sustaining antibacterial properties. The addition amount of these antibacterial agents is preferably 0.05 to 5% by weight. The average particle size of these antibacterial agents is preferably 1 to 50 μm. A commercially available inorganic antibacterial agent “Zeomic” manufactured by Sinanen Zeomic Co., Ltd. is also a preferable antibacterial agent.

  In the matted laminated polyester film 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, electrification are necessary. An appropriate amount of an inhibitor, a plasticizer, 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 the film configuration of the matted laminated polyester film of the present invention, it is necessary to have at least a two-layer configuration of A / B, but the surface is easily slippery, thermal adhesive, tacky, heat resistant, weather resistance, Layers for imparting new functions such as antibacterial properties may be further laminated, and the lamination thickness ratio of each layer can be arbitrarily set. As a layer to which functionality is imparted, for example, a layer obtained by imparting antibacterial properties to the C layer may be used, and a C / A / B configuration may be employed.

  The matted laminated polyester film of the present invention preferably has an elastic modulus in the range of 1 to 1000 MPa at 25 ° C. When the elastic modulus is in such a preferable range, when used in the form of a film, the deformation is small, there is no problem in handling, and the low temperature formability is excellent. In order to make the elastic modulus in the range of 1 to 1000 MPa at 25 ° C., for example, the content of the long-chain aliphatic dicarboxylic acid is changed as necessary, or a long-chain aliphatic dicarboxylic acid having a high flexibility effect is used. A method is mentioned.

  The matted laminated polyester film of the present invention may be an unstretched film or a stretched film. The stretched film may be either a uniaxially stretched film stretched in either the longitudinal direction or the width direction of the film, or a biaxially stretched film stretched in both the longitudinal direction or the width direction of the film. The unstretched film is more easily embossed and is preferable, but the plane orientation coefficient (fn) of a preferable film in the case of an unstretched film is 0.00 to 0.05.

  Here, the plane orientation coefficient (fn) is a value calculated from the refractive index (Nx, Ny, Nz, respectively) in the film longitudinal direction, width direction, and thickness direction measured using an Abbe refractometer or the like by the following equation. It is.

Plane orientation coefficient: fn = (Nx + Ny) / 2−Nz
In addition, the matted laminated polyester film of the present invention has a thermal shrinkage of at least one direction at a molding temperature of −10 to 10% from the viewpoint of suppressing thermal adhesiveness and workability, particularly film wrinkling during processing. A range is preferable. 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 film surface swelling to impair the appearance, peeling from the base material, or distorting printing.

  The thickness of the matted laminated polyester film of the present invention can be freely determined according to the intended use. The thickness is usually preferably in the range of 0.5 to 1000 μm, more preferably 1 to 500 μm, and still more preferably 5 to 200 μm from the viewpoint of film formation stability.

  The matted laminated polyester film of the present invention can be improved in thermal adhesiveness and printability as necessary by performing surface treatment such as corona discharge treatment. 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.

  In the matted laminated polyester film of the present invention, the surface glossiness of the layer A disposed on at least one outermost surface is 0% or more and less than 50%, preferably 0% or more and less than 45%, more preferably 0% or more. Preferably it is less than 40%. If the surface glossiness exceeds 50%, the matte laminated film has insufficient matte properties. Further, since the surface of the layer A functions as a matte film, the surface gloss is preferably as low as possible if it is less than 50%, but there is no particular lower limit, but in practice it is difficult to make it less than 2%.

  In the matted laminated polyester film of the present invention, the thickness of the A layer having a surface glossiness of less than 50% disposed on at least one outermost surface is not particularly limited, but is preferably 10 to 40 μm. ˜30 μm is more preferred. When the thickness of the A layer is, for example, less than 10 μm when bonded to vinyl chloride, the matted film is easily broken during embossing, and the barrier property of the plasticizer in the vinyl tends to be deteriorated. On the other hand, if it exceeds 40 μm, it is not preferable in terms of flexibility, bending wrinkles, curling and cost.

  The matted laminated polyester film of the present invention can be obtained by a melt extrusion method such as a T-die method or an inflation method. For example, when a film is obtained by the T-die method, it is an important condition to quench the extruded film. When it is gradually cooled, the glossiness becomes large and may be insufficient as a matte film. Here, the rapid cooling means that the air gap of the die is reduced and the die is rapidly cooled by a cast roll using an air slit.

  A typical example of the use of the matted laminated polyester film of the present invention is one in which the matted laminated polyester film of the present invention is laminated on a wallpaper substrate. Here, the wallpaper base material is a laminate made of flame retardant paper, non-woven fabric, glass fiber, etc., laminated with polyvinyl chloride, polyolefin, etc. by the calendar method, coating method, etc., and printed on these laminates. In addition, by adding a foaming agent to the polyvinyl chloride, polyvinyl chloride, polyvinyl chloride decorative panel, polyvinyl chloride steel plate, polyvinyl chloride incombustible plate, 1.5 to 15 times expanded, A generic term for polyvinyl chloride decorative panels.

  The matted laminated polyester film of the present invention is laminated with a wallpaper base material and effectively used as a laminate. Examples of the wallpaper base material include polyvinyl chloride, in particular, polyvinyl chloride containing a plasticizer, polyolefin (polyethylene, polypropylene, etc.), polystyrene, polyester, polyamide, etc., preferably polyolefin and polyvinyl chloride.

  Examples of the method for obtaining a laminate of the matted laminated polyester film and the wallpaper substrate of the present invention include dry lamination and heat lamination, and the wallpaper substrate is bonded to the B layer side of the matted laminated film. When the wallpaper base material is polyvinyl chloride, it is preferably thermally bonded simultaneously with embossing. A range of 100 to 200 ° C. is widely used as the thermal bonding temperature. In particular, the heat bonding temperature of the low-foaming wallpaper substrate is preferably in the range of 100 to 160 ° C, and the heat bonding temperature of the high-foaming wallpaper substrate is preferably in the range of 130 to 200 ° C. When the wallpaper substrate is polyolefin, a method of bonding using an adhesive is preferable.

  The laminate (wallpaper) of the present invention thus obtained has no change in the adhesive strength even after long-term use, and further maintains the functions of stain resistance, chemical resistance and embossing. When the inorganic filler (d) is blended with the polyester layer, it is very useful as wallpaper without matte return when heated.

  The matted laminated polyester film of the present invention can also be used as various industrial materials and packaging materials that require formability by a single sheet or a composite sheet. As the composite sheet, for example, it can be used by being bonded to a base material such as metal, wood, paper, resin sheet or resin plate.

  As specific applications, conventional flexible films, applications where easy-molded films have been used, for example, packaging films, wrap films, stretch films, partition films, films for building materials such as wallpaper and plywood decorative sheets, preferably Examples include, but are not limited to, a wallpaper film.

Hereinafter, the present invention will be described in detail by way of examples. Various characteristics were measured and evaluated by the following methods.
(1) Composition ratio of monomer, dimer and trimer in long-chain aliphatic dicarboxylic acid (derivative) Analyzing long-chain aliphatic dicarboxylic acid (derivative) by high-performance liquid chromatography, the peak of each component The composition ratio was determined from the area. Although measurement conditions can be implemented by a known method, an example is shown below.

Column: Interstil ODS-3 2.0 mmφ × 250 mm
Mobile phase: H ₃ PO ₄ aqueous solution / methanol = 80 / 20- (20 min)
20 / 80- (40min)
Flow rate: 0.4 mL / min
Column temperature: 45 ° C
Detector: Photodiode array (200 to 400 nm)
The chromatogram uses 21512. Here, the composition ratio of the monomer, dimer and trimer in the long-chain aliphatic dicarboxylic acid (derivative) in the film can be determined as follows. The long-chain aliphatic dicarboxylic acid is separated by separating the layers by scraping the A layer and the B layer of the film, and further using chromatography such as gel permeation chromatography (GPC) or nuclear magnetic resonance measurement (NMR). A method of identifying the (derivative) and determining the composition ratio of the monomer, dimer, and trimer can be considered.
(2) Intrinsic viscosity of polyester Polyester was dissolved in orthochlorophenol and measured at 25 ° C.
(3) Thermal characteristics (DSC)
Using a differential scanning calorimeter DSCII type manufactured by Seiko Instrument Co., Ltd., 5 mg of the sample was heated at a rate of 10 ° C./min, and the glass transition temperature (Tg), crystallization temperature (Tc), melting point (Tm), crystal The heat of fusion (ΔHm) was determined. These numerical values are values obtained from the first heating step. Further, the crystallization rate ΔTcg was determined by the following equation.

ΔTcg = Tc−Tg
Here, when obtaining Tg, Tc, Tm, ΔTcg, and ΔHm of each layer from the film, each layer was separated by, for example, scraping off the A layer and the B layer, and then measured by the method described above.
(4) Film formation stability The stability at the time of film formation of a laminated polyester film was determined according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (good): The film can be stably formed with a constant discharge rate.
△ (possible): Although discharge becomes unstable temporarily, there is almost no problem in film forming property.
X (impossible): The discharge amount is clearly unstable, and stable film formation is difficult.
(5) Matting property of the film The matting property of the matted laminated polyester film is determined by using a digital variable angle gloss meter UGD-5D manufactured by Suga Test Instruments Co., Ltd., and changing the incident angle and detection angle from the normal direction of the film surface. 20 arbitrary points on the A layer surface side of the film were measured at 60 °, and the average value of glossiness was determined. The average value of glossiness was judged according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (Good): Glossiness less than 10%
Δ (possible): Glossiness in the range of 10 to 50%,
X (impossible): The glossiness exceeds 50%.
(6) Embrittlement over time of film (breaking elongation)
The film 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 Corporation. 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 determined and the embrittlement with time was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (good): the elongation at break exceeds 100%,
Δ (possible): one having a breaking elongation in the range of 10 to 100%,
X (impossible): The elongation at break is less than 10%.
(7) Film embossability (formability)
While the film was preheated at 130 ° C., an embossing roll (embossed shape 4 mm square, depth 2 mm) was passed at a pressure of 4.9 × 10 ⁴ N / m ² and a speed of 4 m / min. Transferred to the layer side. The surface on the embossing side was observed using an ultra-deep shape measuring microscope (manufactured by Keyence Co., Ltd.), and the area (S1 (i)) of the top surface of one convex portion was determined. Then, the concave part of the film surface to which the convex part observed above was transferred was observed with an ultra-deep shape measuring microscope, and the area (S2 (i)) of the concave part bottom surface of the film 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 embossability was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (good): transfer rate exceeding 70%,
Δ (possible): transfer rate in the range of 40-70%,
X (Not possible): Transfer rate is less than 40%.
(8) Water vapor barrier property (gas barrier property)
Using a water vapor transmission meter “PERMATRAN” W3 / 31 manufactured by Modern Control Co., Ltd., the average value of the water vapor transmission rate measured at a measurement number n = 5 under the conditions of a temperature of 37.8 ° C. and a relative humidity of 100% is g It was shown in units of / (m ² · day). The measurement surface was measured from the A layer surface side. From the average value of the water vapor permeability measured for the water vapor permeability, the following evaluation criteria were used. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (Good): Water vapor permeability is less than 100 g / (m ² · day),
Δ (possible): Water vapor permeability in the range of 100 to 200 g / (m ² · day),
X (impossible): Water vapor permeability exceeding 200 g / (m ² · day).
(9) Preparation of wallpaper As wallpaper, 100 parts by weight of building paper (“KPK # 120” manufactured by Yupo Corporation), guanidine sulfamate as a flame retardant (“Apinon-145” manufactured by Sanwa Chemical Co., Ltd.) Flame retardant paper impregnated with 20 parts by weight, 100 parts by weight of vinyl chloride resin (“Paste Resin P450D” manufactured by Vitec Co., Ltd.), and calcium carbonate as filler (“Nanox # 30” manufactured by Maruo Calcium Co., Ltd.) 50 parts by weight, bis (2-ethylhexyl) phthalate (“DOP” manufactured by Daihachi Chemical Co., Ltd.) as a plasticizer, and titanium oxide (“KRONOS KA-20 manufactured by Titanium Industry Co., Ltd.) as a pigment “) 20 parts by weight, 3 parts by weight of tricresyl phosphate (“ TCP ”manufactured by Daihachi Chemical Co., Ltd.) as a flame retardant, and Ca / Zn-based stabilizer (Japan) 2 parts by weight of “CZ series” manufactured by Chemical Industry Co., Ltd., 2 parts by weight of p, p′-oxybisbenzenesulfonyl hydrazide (“Cermic S” manufactured by Sankyo Kasei Co., Ltd.) as a foaming agent, and as an antibacterial agent After laminating a mixture of 2 parts by weight of an organometallic pyridine-based compound (“Amorden TMS-32” manufactured by Daiwa Chemical Industry Co., Ltd.), heat treatment is performed at 230 ° C. for 1 minute to foam PVC, resulting in low foaming. A polyvinyl chloride wallpaper base material was obtained, and the expansion ratio was 3 times the thickness before foaming.

  Moreover, the addition amount of the foaming agent was doubled to 4 parts by weight to obtain a highly foamed polyvinyl chloride wallpaper base material having a foaming ratio of 5 times. The expansion ratio was determined by measuring the thickness before foaming with a thickness gauge and the thickness after foaming at 10 points, obtaining the average value, and determining the expansion ratio.

Next, for the two types of wallpaper, after mating the B layer side of the matted laminated polyester film and the polyvinyl chloride resin surface laminated on the paper, the low-foam polyvinyl chloride uses an embossing roll at 150 ° C, 14.7 × 10 ⁴ N / m ² , speed 4 m / min), highly foamed polyvinyl chloride is pressure-bonded with an embossing roll at 120 ° C. (pressure 4.9 × 10 ⁴ N / m ² , speed 4 m / min). After that, heat bonding and embossing were performed at the same time, and two types of wallpaper, a low foam wallpaper and a high foam wallpaper, were obtained. The embossing roll used was an embossed 4 mm square with a depth of 2 mm.
(10) Contamination resistance For the two types of wallpaper produced in (9) above, oil-based magic (“Magic Ink” (registered trademark) bold black), soy sauce (manufactured by Kikkoman Corporation) on the film side (A layer) Kikkoman dark mouth}, coffee, crayons, curry and starch paste were applied or drawn in a size of 2 cm × 2 cm, left at a temperature of 23 ° C. and a humidity of 65% RH for 24 hours, and then wiped off with gauze with ethyl alcohol. Contamination resistance was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (Good): Both types of wallpaper have no trace of contaminants on the film surface.
△ (possible): Both types of wallpaper have traces of contaminants on the film surface but have no practical problems.
X (impossible): Both types of wallpaper leave traces of contaminants on the film surface.
(11) Chemical resistance For the two types of wallpaper produced in (9) above, add a stock solution of chlorinated detergent (made by Kao Corporation: “Kitchen Hiter”) to the film side (A layer) in the gauze. Then, after leaving for 24 hours at a temperature of 23 ° C. and a humidity of 65% RH, the gauze was removed, carefully wiped with a new gauze, further wiped with water and wiped with air. Chemical resistance was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (Good): The two types of wallpaper have no traces of chemicals on the film surface.
△ (possible): Both types of wallpaper have chemical marks on the film surface, but there is no practical problem.
× (No): Both types of wallpaper have holes on the film surface.
(12) Thermal adhesiveness with polyvinyl chloride About the two types of wallpaper produced in (9) above, cut into a 3 cm width x 10 cm length, peel off the surface layer film, and use Tensilon manufactured by Orientec Co., Ltd., measuring temperature 23 ° C. The average value of the tensile rate of 200 mm / min and the number of measurements n = 10 was determined, and the thermal adhesion between the surface film and the vinyl chloride layer was evaluated according to the following criteria. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (good): The film peeled at the interface between the surface film and the foamed PVC, and the adhesive strength exceeded 2.9 × 10 ³ N / 30 mm, or the foamed PVC layer peeled off.
△ (acceptable): peeling at the interface of the surface layer film and the foamed PVC, but the adhesive strength is in the range of ^{1.5 × 10 3 /30mm~2.9×10 3 / 30mm} , as no practical problem,
× (poor): peeling at the interface of the surface layer film and the foamed PVC, the adhesion strength is 1.5 × ¹⁰ 3 / 30mm less than one.
(13) Matting property after embossing The matting property after embossing is about the two types of wallpaper produced in the above (9), the surface of the wallpaper is the digital variable angle gloss meter UGD- manufactured by Suga Test Instruments Co., Ltd. Using 5D, the incident angle and the detection angle were measured at 20 arbitrary positions at 60 ° from the normal direction of the film surface, and the average value and standard deviation of the glossiness were obtained. The standard deviation was adopted because glossiness variation increases when matte returns occur in embossing. Judgment was made according to the following criteria from the average value and standard deviation of glossiness. If it is (circle) and (triangle | delta), it is suitable as what satisfies this invention.
○ (good): average glossiness of less than 10% and standard deviation of less than 1%,
Δ (possible): the average glossiness is in the range of 10 to 50%, the average glossiness is less than 10%, and the standard deviation is more than 1%,
X (impossible): The average glossiness exceeds 50%.
(14) Comprehensive evaluation Excellent film-forming stability, stain resistance, chemical resistance, embossability, thermal adhesiveness with PVC, matteness, embrittlement over time, and practicality as a wallpaper surface layer film Was evaluated as ◯, a slightly inferior one as Δ, and an inferior one as ×.
[Polymerization of aromatic polyester]
{Synthesis of Polyester 1 (PET)}
To a mixture of 91.5 parts by weight of dimethyl terephthalate and 58.5 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 heated to increase the temperature by a conventional method. An exchange 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 prepare a polyester having an intrinsic viscosity of 0.65. The obtained polymer had Tg of 80 ° C., Tc of 137 ° C., and ΔTcg of 56 ° C.
{Synthesis of Polyester 2 (PBT)}
To a mixture of 77.8 parts by weight of dimethyl terephthalate and 72.2 parts by weight of 1,4-butanediol, 0.05 parts by weight of tetrabutyl titanate and 0.02 parts by weight of IRGANOX 1010 (Ciba Specialty Chemicals) were added. Finally, the temperature was 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 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 produce a polyester having an intrinsic viscosity of 0.85. The polymer obtained had a Tg of 30 ° C., a Tc of 41 ° C., and a ΔTcg of 11 ° C.
{Synthesis of Polyester 3 (PPT)}
To a mixture of 84.1 parts by weight of dimethyl terephthalate and 65.9 parts by weight of 1,3-propanediol, 0.06 part by weight of tetrabutyl titanate is added, and finally the temperature is raised to 220 ° C. to conduct a transesterification reaction. It was. 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 produce a polyester having an intrinsic viscosity of 0.70. The polymer obtained had a Tg of 50 ° C., a Tc of 74 ° C., and a ΔTcg of 24 ° C.
{Synthesis of Polyester 4 (PET / I)}
Charge 80.0 parts by weight of dimethyl terephthalate, 11.4 parts by weight of dimethyl isophthalate, 58.5 parts by weight of ethylene glycol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX1010FP, and increase from 150 ° C to 210 ° C. Transesterification was carried out in accordance with a conventional method while warming, 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 0.022 part by weight of IRGANOX 1010FP were added, followed by polycondensation. The reaction system was transferred to a reaction vessel, and the pressure of the reaction system was gradually reduced while heating and heating, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1.33 × 10 ² Pa. 5 mol% copolymer polyester resin was obtained.
(Synthesis of polyester 5-6)
Polyesters 5-6 listed in Table 1 were synthesized in the same manner as for polyester 4.
[Polymerization of aliphatic polyester]
(Synthesis of copolymer polyester 1)
A mixture of 77.7 parts by weight of dimethyl terephthalate, 19.7 parts by weight of ethylene glycol, 42.5 parts 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 parts by weight of trimethyl phosphoric acid was added. Ten minutes later, 0.055 parts by weight of tetrabutyl titanate, 0.022 parts by weight of IRGANOX 1010FP, 50 ° C. in advance. A dimer acid (PRIPOL 1025: manufactured by Unikema) heated to 7.3 parts by weight / 1,4-butanediol 2.0 parts by weight / ethylene glycol 0.7 parts by weight was added to the slurry. 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 0.69 and a dimer acid of 3 mol%.
(Synthesis of copolymer polyester 2)
A copolyester 2 listed in Table 1 was synthesized in the same manner as the copolyester 1.
(Synthesis of copolymer polyester 3)
From 150 ° C. to 210 ° C., 54.7 parts by weight of dimethyl terephthalate, 18.0 parts by weight of ethylene glycol, 20.3 parts by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX1010FP are charged. Transesterification was conducted 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, and 10 minutes later, 0.055 part by weight of tetrabutyl titanate, 0.022 part by weight of IRGANOX 1010FP, 50 parts in advance. Dimer acid (PRIPOL 1098: manufactured by Unikema) heated to 0 ° C. was added 41.8 parts by weight / 11.4 parts by weight of 1,4-butanediol / 3.8 parts by weight of ethylene glycol. 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 copolyester 3 having an intrinsic viscosity of 0.85 and a dimer acid of 20 mol%.
(Synthesis of copolymer polyester 4)
Charged 73.2 parts by weight of dimethyl terephthalate, 67.4% by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX1010FP, and the usual method while raising the temperature from 150 ° C to 210 ° C Then, 0.042 parts by weight of trimethyl phosphoric acid was added, 0.055 parts by weight of tetrabutyl titanate, 0.022 parts by weight of IRGANOX 1010FP, dimer acid (PRIPOL 1025 heated to 50 ° C. in advance). 6.9 parts by weight / 1,4-butanediol 2.5 parts by weight of mixed slurry 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 0.95 and a dimer acid of 3 mol%.
(Synthesis of copolymer polyester 5)
Copolyester 5 listed in Table 1 was synthesized in the same manner as copolymer polyester 4.
(Synthesis of copolymer polyester 6)
A mixture of 58.4 parts by weight of dimethyl terephthalate and 41.7 parts by weight of 1,3-propanediol was charged with 0.04 parts by weight of tetrabutyl titanate and 0.016 parts by weight of IRGANOX1010FP, and the temperature was raised from 150 ° C to 210 ° C. However, 0.042 parts by weight of trimethyl phosphoric acid was added according to a conventional method, and 10 minutes later, 0.055 parts by weight of tetrabutyl titanate and 0.022 parts by weight of IRGANOX 1010FP were preliminarily heated to 50 ° C. PRIPOL 1098 (manufactured by Unikema)) 36.6 parts by weight / 1,4-butanediol 13.3 parts by weight of mixed slurry 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 6 having an intrinsic viscosity of 0.85 and a dimer acid of 17 mol%.
(Synthesis of copolymer polyester 7)
Prepared with 66.3 parts by weight of dimethyl terephthalate, 65.8% by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate and 0.016 parts by weight of IRGANOX1010FP, and while raising the temperature from 150 ° C. to 210 ° C. Then, 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 1010FP, dodecanedioic acid 13 heated in advance to 50 ° C. 13 .1 part by weight / 1,4-butanediol 4.8 parts by weight mixed slurry 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 7 having an intrinsic viscosity of 0.90 and dodecanedioic acid of 13 mol%.
(Synthesis of copolymer polyester 8)
From 150 ° C., 41.4 parts by weight of dimethyl terephthalate, 13.2 parts by weight of dimethyl isophthalate, 48.7% by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of IRGANOX1010FP Transesterification was carried out according to a conventional method while raising the temperature to 210 ° C., and then 0.042 part by weight of trimethyl phosphoric acid was added. Ten minutes later, 0.055 part by weight of tetrabutyl titanate, 0.022 part by weight of IRGANOX 1010FP, 34.2 parts by weight of dimer acid (PRIPOL 1098: manufactured by Unikema) heated to 50 ° C./12.4 parts by weight of 1,4-butanediol mixed slurry 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 copolyester 8 having an intrinsic viscosity of 0.95, isophthalic acid 20 mol%, and dimer acid 17 mol%.
(Synthesis of copolyester 9-12)
Copolyesters 9 to 12 shown in Table 1 were synthesized in the same manner as the copolyester 9.
{Preparation of particle master 1 (MS-1)}
89 parts by weight of polyester 2, 10 parts by weight of talc (Nippon Talc Co., Ltd. ultrafine talc SG-2000, average particle size 1.0 μm, whiteness 97%), antibacterial agent, inorganic antibacterial manufactured by Sinanen Zeomic Co., Ltd. A mixture of 1 part by weight of the agent “Zeomic” was kneaded at 260 ° C. using a vent type different-direction twin screw extruder to prepare a particle master 1 of 1% by weight of antibacterial agent and 10% by weight of talc.
{Preparation of particle master 2 (MS-2)}
89 parts by weight of copolymerized polyester 2, 10 parts by weight of talc (Nippon Talc Co., Ltd. ultrafine talc SG-2000, average particle size 1.0 μm, whiteness 97%), and antibacterial agent manufactured by Sinanen Zeomic Co., Ltd. A mixture of 1 part by weight of the inorganic antibacterial agent “Zeomic” was kneaded at 260 ° C. using a vented different-direction twin screw extruder to prepare a particle master 2 of 1% by weight of the antibacterial agent and 10% by weight of talc.
{Preparation of particle master 3 (MS-3)}
Polypropylene {"Prime Polypro" F102W manufactured by Mitsui Chemicals Co., Ltd., MI 2.0 g / 10 min (230 ° C., load 2.13 kg) density 0.91 g / cm ³ } 90 parts by weight, Nihon Talc Co., Ltd. ultrafine talc (SG-2000, average particle size 1.0 μm, whiteness 97%) 10 parts by weight of a mixture was kneaded at 220 ° C. using a 30 mmφ vented different direction two-extruder to produce a 10% by weight talc particle master 3. did.
{Preparation of particle master 4 (MS-4)}
89 parts by weight of polyester 2, 10 parts by weight of silicon dioxide (“Silysia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle size 2.5 μm), as an antibacterial agent, inorganic antibacterial agent “Zeomic” 1 manufactured by Sinanen Zeomic Co., Ltd. Part by weight of the mixture was kneaded at 260 ° C. using a vent type different-direction two-extruder having a diameter of 30 mmφ to prepare 1% by weight of an antibacterial agent and 10% by weight of silicon dioxide.

Table 1 shows the compositions of polyester, copolymer polyester, and particle master used in Examples and Comparative Examples.
{Preparation of particle master 5 (MS-5)}
89 parts by weight of polyester 3, 10 parts by weight of silicon dioxide (“Silysia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle size 2.5 μm), and as an antibacterial agent, an inorganic antibacterial agent “Zeomic” 1 manufactured by Sinanen Zeomic Co., Ltd. Part by weight of the mixture was kneaded at 260 ° C. using a 30 mmφ vented different-direction two-extruder to produce 1% by weight of an antibacterial agent and 10% by weight of silicon dioxide.

  Table 1 shows the compositions of polyester, copolymer polyester, and particle master used in Examples and Comparative Examples.

In Table 1 above,
DMT: terephthalic acid component DMI: isophthalic acid component C36: dimer acid component (main chain carbon number 36)
DDO: dodecanedioic acid component DMA: adipic acid component SSIA: sodium sulfoisophthalate component EG: ethylene glycol component BG: butanediol component PG: propanediol component (Example 1)
Vented bi-directional biaxial extrusion using a mixture of 30% by weight of polyester 4, 60% by weight of particle master MS-1 and 10% by weight of copolyester 5 as the polyester of layer A and set at an extrusion temperature of 260 ° C. Vent type bi-directional extruder B (two vent ports, L) using copolymer polyester 9 as polyester for layer B in machine A (2 vent ports, L / D = 70) and set to 230 ° C / D = 70), set to 250 ° C, led to a double-layer T-die die with a slit gap of 0.5mm, extruded into a film, and using a suction chamber, slit air blowing method, satin casting at a temperature of 55 ° C It was cooled and solidified with a drum to produce a matted laminated polyester film having a thickness of 15 μm.

  The matted laminated polyester film was able to be stably formed, was not embrittled with time, and was excellent in handleability. Moreover, as shown in Table 3, it was excellent in matteness, embossing property, and water vapor | steam barrier property.

  Next, foamed PVC for wallpaper was produced. As a flame retardant for 100 parts by weight of paper, guanidine sulfamate (manufactured by Sanwa Chemical Co., Ltd. "Apinon-145" 20 parts by weight impregnated flame retardant paper for backing, 100 parts by weight of vinyl chloride resin, as a filler, 50 parts by weight of calcium carbonate (“Nanox # 30” manufactured by Maruo Calcium Co., Ltd.), 55 parts by weight of bis (2-ethylhexyl) phthalate (“DOP” manufactured by Daihachi Chemical Co., Ltd.) as a plasticizer, and as a pigment 20 parts by weight of titanium oxide (“KRONOS KA-20” manufactured by Titanium Industry Co., Ltd.), 3 parts by weight of tricresyl phosphate (“TCP” manufactured by Daihachi Chemical Co., Ltd.) as a flame retardant, Ca as a stabilizer / Zn stabilizer (“CZ series” manufactured by Nissan Chemical Industries, Ltd.) 2 parts by weight, p, p′-oxybisbenzenesulfonylhydrazide (“Cell” manufactured by Sankyo Kasei Co., Ltd.) as a foaming agent Iku S "), 2 parts by weight, and a mixture of 2 parts by weight of an organometallic pyridine compound (" Amorden TMS-32 "manufactured by Daiwa Chemical Industry Co., Ltd.) as an antibacterial agent. To obtain foamed PVC for wallpaper.

  Next, according to the above (9) wallpaper production method, two types of wallpaper, low foam wallpaper and high foam wallpaper, were obtained.

As shown in Table 3, the properties of the obtained film and wallpaper showed excellent matteness, stain resistance, chemical resistance, and thermal adhesiveness with PVC after embossing.
(Examples 2-9)
The polyester for the A layer and the polyester for the B layer were prepared as shown in Table 2 to prepare a matted laminated polyester film having a thickness of 15 μm.

  In addition, according to the above (9) wallpaper production method, two types of wallpaper, low foam wallpaper and high foam wallpaper, were obtained.

  The properties of the obtained film and wallpaper are summarized in Table 3, respectively.

  In the wallpaper film, the wallpaper films obtained in Examples 1 to 4, Example 6 and Example 8 are films excellent in all of embrittlement with time, matteness, embossing and water vapor barrier properties. there were.

  The films obtained in Example 5 and Example 9 were practically used although they were slightly inferior in matte properties, and were excellent in all of embrittlement with time, embossing properties, and water vapor barrier properties.

  Further, the wallpaper film obtained in Example 7 was a practical level although it was slightly inferior in embossing property and was excellent in all of embrittlement with time, matting property and water vapor barrier property.

  As wallpaper characteristics, the wallpaper obtained in Example 1, Example 3, and Examples 6 to 8 is resistant to contamination, chemical resistance, low foam polyvinyl chloride and high foam polyvinyl chloride, The wallpaper was excellent in both mattness after embossing.

Moreover, the wallpaper obtained in Example 2, Examples 4 to 5 and Example 9 is a practical level although it is slightly inferior in terms of thermal adhesion with highly foamed polyvinyl chloride and matte properties after embossing, The wallpaper was excellent in stain resistance, chemical resistance, low-foamed polyvinyl chloride and thermal adhesiveness, and matte properties after embossing.
(Comparative Example 1)
A single-layer unstretched polyester film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that polyester 2 was used for layer A and polyester B was not used as layer A polyester.

  In addition, according to the above (9) wallpaper production method, two types of wallpaper, low foam wallpaper and high foam wallpaper, were obtained.

As shown in Table 3, the properties of the obtained film are excellent in water vapor barrier properties, but slightly inferior in embrittlement with time, inferior in matte properties, and inferior in embossability because the film is crystallized. It was unsuitable as a film for wallpaper. In terms of wallpaper characteristics, the stain resistance and chemical resistance were good, but since there was no adhesive layer, it did not adhere to low-foam polyvinyl chloride and high-foam polyvinyl chloride.
(Comparative Example 2)
A laminated unstretched polyester film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that polyester 1 was used as the polyester for the A layer and polyester 6 was used as the polyester for the B layer.

  In addition, according to the above (9) wallpaper production method, two types of wallpaper, low foam wallpaper and high foam wallpaper, were obtained.

As shown in Table 3, the properties of the obtained film were unsuitable as a film for wallpaper, although the water vapor barrier property was excellent, but the embossing property was slightly inferior, the embrittlement with time and the matte property were inferior. . The wallpaper has excellent stain resistance and chemical resistance, but TmB exceeds 210 ° C, so it is slightly inferior in thermal adhesiveness with low foamed polyvinyl chloride and thermal adhesiveness with highly foamed polyvinyl chloride. Was inferior.
(Comparative Example 3)
As the polyester of layer A, a mixture of 40% by weight of polyester 1, 57% by weight of polyester 2 and 3% by weight of copolymer polyester 2 was used. Except for the above, a single-layer unstretched polyester film having a thickness of 15 μm was produced in the same manner as in Example 1.

  In addition, according to the above (9) wallpaper production method, two types of wallpaper, low foam wallpaper and high foam wallpaper, were obtained.

As shown in Table 3, the properties of the obtained film were excellent in embossing and water vapor barrier properties and slightly inferior in matte properties, but poor in embrittlement with time, difficult to handle, and unsuitable as a wallpaper film. It was. Further, although the wall paper was excellent in stain resistance and chemical resistance, it did not adhere to low foamed polyvinyl chloride and high foamed polyvinyl chloride because there was no adhesive layer.
(Comparative Example 4)
A laminated unstretched polyester film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the copolymer polyester 4 was used as the polyester for the A layer and the copolymer polyester 3 was used as the polyester for the B layer.

  In addition, (9) two types of wallpaper, a low-foam wallpaper and a high-foam wallpaper, were obtained in accordance with the wallpaper production method.

As shown in Table 3, the properties of the obtained film are excellent in embrittlement with time and water vapor barrier property, but are poor in embossing property and unsatisfactory as a film for wallpaper because the matting property and TgA of the A layer are too low. It was appropriate. The wallpaper characteristics were excellent in stain resistance, chemical resistance and thermal adhesiveness with low foamed polyvinyl chloride and highly foamed polyvinyl chloride, but inferior in matte properties after embossing.
(Comparative Example 5)
As a polyester of layer A, a mixture of 40% by weight of polyester 1, 57% by weight of polyester 2, and 3% by weight of copolymer polyester 2 was used. Thus, a single-layer unstretched polyester film having a thickness of 15 μm was produced.

  In addition, according to the above (9) wallpaper production method, two types of wallpaper, low foam wallpaper and high foam wallpaper, were obtained.

As shown in Table 3, the properties of the obtained film were excellent in stain resistance and chemical resistance, but were inferior in matteness and unsuitable as a wallpaper film. In terms of wallpaper characteristics, although the stain resistance, chemical resistance and adhesion to low-foamed polyvinyl chloride are excellent, TmB is less than 210 ° C, but ΔHmB exceeds 30 J / g. It was inferior in thermal adhesiveness with vinyl.
(Comparative Example 6)
As the wallpaper surface layer film, the adhesive layer of Kuraray Co., Ltd. ethylene-vinyl alcohol copolymer (EVOH) film “EVAL HF-ME” (with adhesive layer) is removed with absorbent cotton using methyl ethyl ketone. It was.

  The “EVAL” film was excellent in embrittlement over time, matteness and embossing properties, but was slightly inferior in water vapor barrier properties. The wallpaper had excellent matte properties after embossing, but was slightly inferior in stain resistance and inferior in chemical resistance. Moreover, since the adhesive layer was removed, the adhesiveness with the low foamed polyvinyl chloride and the highly foamed polyvinyl chloride was poor.

  Table 2 shows the contents of the A layer and B layer in the above Examples and Comparative Examples, and Table 3 shows the evaluation results of film characteristics and wallpaper characteristics.

  The matted laminated polyester film of the present invention is a single sheet or a composite sheet, taking advantage of excellent properties such as stain resistance, chemical resistance, moldability, thermal adhesiveness, matteness, embossing, and water vapor barrier properties. Therefore, it can be used as various industrial materials and packaging materials that require moldability. In the composite sheet, it can be used by being bonded to a base material such as metal, wood, paper, resin sheet or resin plate.

  As specific applications, conventional flexible films, applications where easy-molded films have been used, for example, packaging films, wrap films, stretch films, partition films, films for building materials such as wallpaper and plywood decorative sheets, preferably Examples include wallpaper films.

Claims (8)

  A laminated polyester film having at least two layers of an A layer and a B layer, wherein the A layer comprises 20 to 98 parts by weight of the polyester (a) and 2 to 40 parts by weight of the aliphatic dicarboxylic acid copolyester (b). The layer B is a copolyester having a melting point TmB of 120 to 210 ° C. and a crystal melting heat quantity ΔHmB of 5 to 30 J / g, and a polyester having a glass transition temperature TgA of 30 to 70 ° C. A matted laminated polyester film, wherein the surface glossiness of the layer A surface located on the surface is less than 50%.   In the polyester of the A layer, the thermoplastic resin (c) and / or the inorganic filler (d) is 40 parts by weight or less with respect to 100 parts by weight in total of the polyester (a) and the aliphatic dicarboxylic acid copolymerized polyester (b). The matted laminated polyester film according to claim 1, which is contained.   The matted laminated polyester film according to claim 1 or 2, wherein the aliphatic dicarboxylic acid copolyester (b) of the A layer has a long-chain aliphatic dicarboxylic acid component. The matted laminated polyester film according to any one of claims 1 to 3, wherein the copolyester constituting the B layer satisfies the following (1) and (2).
(1) A copolymer polyester containing 60 to 99 mol% of an aromatic dicarboxylic acid component and 1 to 40 mol% of a long-chain aliphatic dicarboxylic acid component with respect to all dicarboxylic acid components.
(2) A copolymer polyester containing at least one glycol component having less than 10 carbon atoms with respect to the glycol component.   In the aliphatic dicarboxylic acid copolyester (b) of the A layer and / or the long chain aliphatic dicarboxylic acid component in the copolyester constituting the B layer, the dimer dicarboxylic acid content is 70 to 90 wt. %, And the content of the trimer dicarboxylic acid is 10 to 30% by weight.   The matted laminated polyester film according to any one of claims 3 to 5, wherein the long-chain aliphatic dicarboxylic acid component is a dimer acid or a dimer acid derivative.   A wallpaper comprising: the matted laminated polyester film according to any one of claims 1 to 6 and a wallpaper base material laminated so that an A layer of the matted laminated polyester film is an outer surface.   The wallpaper according to claim 7, wherein the wallpaper substrate includes a polyolefin resin layer or a polyvinyl chloride resin layer.