JPH04293935A - Sheet for interior decoration - Google Patents

Abstract

PURPOSE:To obtain the title sheet which has necessary flexibility, desirable breaking extension and desirable residual stress and does not produce any noxious gases even when burnt by using a flexible film prepared from a copolyester of a specified DELTATcg. CONSTITUTION:A sheet for interior decoration, produced from a flexible film prepared from a copolyester of a DELTATcg of 60 deg.C or below [e.g. a copolyester containing at least two kinds of diol component residues selected from HO-(CH2)2n-OH (wherein (n) is 1-10) as an alcohol component and containing 40-99mol%, based on the total acid component, aromatic dicarboxylic acid residues and 60-1mol% long-chain aliphatic dicarboxylic acid residues) and having a Young's modulus in tension of 0.1-50kg/mm<2>. This sheet has necessary flexibility, desirable breaking extension and desirable residual stress is free from the problem of deterioration due to bleed-out of plasticizer and sanitariness because it is not plasticized, does not produce any noxious gases even when burnt, and is very desirable for use in a large quantity.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interior sheet using a flexible copolyester film.

0002

[Prior Art] Interior sheets used for wallpaper, flooring, etc. have conventionally been made of soft vinyl chloride resin sheets or laminates of this with paper, cloth, other resin films, etc.
Those with printing, coating (for surface protection, static electricity prevention, etc.), graining, embossing, etc. are often used. This interior seat has
It has sufficient flexibility to conform to the shape of walls and floors, and has enough elongation at break to not easily break or wrinkle when stretched to attach to the corners of walls or floors. required. In addition, it is often required that an appropriate amount of stress remain after construction to prevent loosening or peeling.

0003

[Problems to be Solved by the Invention] However, conventional interior sheets using soft vinyl chloride sheets have the following problems.

First, in the case of soft vinyl chloride, the plasticizer migrates to the surface (bleeds out) over time, and the bleed-out plasticizer itself deteriorates the quality of the surface and causes hygiene problems. There is a risk. Furthermore, since the bleed-out plasticizer forms a sticky surface layer, dust may adhere to the surface layer, which may also lead to deterioration in quality and hygiene problems.

[0005] Furthermore, since vinyl chloride does not have very high chemical resistance, stains cannot be removed with organic solvents, leading to problems such as complicating the cleaning process during interior sheet processing and use.

Furthermore, since vinyl chloride contains halogen elements, it generates harmful gases when incinerated. Therefore,
The processing of used interior sheets will be restricted, and as a result, the use of large quantities of soft vinyl chloride sheets as interior sheets will also be restricted due to environmental concerns.

[0007] To solve the above problem, some materials such as polyvinyl fluoride have been used from the viewpoint of flame retardancy, but they are expensive and
Not suitable for general-purpose or mass-use applications.

The present invention focuses on the problems of conventional interior sheets using soft vinyl chloride sheets as described above, and has the necessary flexibility, desirable elongation at break, and stress residual rate, and the use of plasticizers. It is an object of the present invention to provide an interior sheet which is extremely suitable for large-scale use and does not contain plasticizer and does not cause deterioration in quality or hygienic problems due to bleed-out of the plasticizer, and does not generate harmful gases even when incinerated.

[0009]

[Means for Solving the Problems] The interior sheet of the present invention that meets this objective is made of a copolymerized polyester having a ΔTcg of 60°C or less, and a tensile Young's modulus of 0.1 to 50 kg.
/mm2 of flexible film.

The copolyester constituting the flexible polyester film of the present invention has a cold crystallization temperature (Tcc)
and the difference between the glass transition temperature (Tg) (Tcc-Tg)
It is necessary that ΔTcg defined by is 60°C or less, preferably 50°C or less. If ΔTcg is too large, the tensile Young's modulus may increase over time,
This causes problems such as deterioration of flexibility.

[0011] Specific examples of the composition of the copolymerized polyester include the following. That is, as a soft segment, polyoxyalkylene glycol such as polyethylene glycol and polytetramethylene glycol, or HOOC- such as polyε-caprolactone, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, etc.
[CH2] An aliphatic polyester consisting of an aliphatic dicarboxylic acid of n-COOH and an aliphatic and/or alicyclic diol is preferable, and in particular, as a soft segment, an aliphatic polyester containing a long-chain aliphatic dicarboxylic acid is preferable. This is preferable in order to improve flexibility and elongation at break.

[0012] In the present invention, long-chain aliphatic dicarboxylic acids are dicarboxylic acids having an alkylene group having 8 to 60 carbon atoms, such as sebacic acid, eicoic acid, dodecanedioic acid, and dimer acid, particularly those having 10 carbon atoms. A range of 50 to 50 is preferable because it provides good flexibility.

Particularly in the present invention, among long-chain aliphatic dicarboxylic acids, it is preferable to use a long-chain branched aliphatic dicarboxylic acid having a branched structure, and among these, dimer acid is preferably used due to its flexibility and elongation at breakage. It is preferable in terms of improving the degree of strength. Here, dimer acid is a mixture of a chain branched structure and a cyclic branched structure obtained by a dimerization reaction of unsaturated aliphatic carboxylic acid methyl ester such as methyl oleate. but hydrogenated to have a bromine number of 0.05 to 10 g/100 g, preferably,
A ratio of 0.1 to 5 g/100 g is preferable because it has excellent flexibility and elongation at break.

The hard segment of the above-mentioned copolymerized polyester has a melting point of 20
0°C or higher, glass transition temperature 90°C or lower, ΔTcg 8
It is preferable that the temperature is 0°C or lower in order to improve chemical resistance, solvent resistance, etc. Specifically, ethylene terephthalate, butylene terephthalate, cyclohexane dimethylene terephthalate, cyclohexane dimethylene cyclohexane dicarboxylate, butylene-naphthalene Preferably, it is composed of at least one selected from aromatic and/or alicyclic ester units such as dicarboxylate. Among these, those having terephthalic acid residues are particularly preferred because they have good durability.

[0015] Here, the copolymerized polyester preferably used has an intrinsic viscosity of 0.5 to 2.0 dl/g.
, preferably 0.7 to 1.8 dl/g. By setting the intrinsic viscosity within such a range, both film formability and mechanical properties of the polyester film are improved.

Furthermore, the melting point (T
Practically speaking, m) is preferably in the range of 130 to 250°C, more preferably in the range of 140 to 230°C. Further, the glass transition temperature (Tg) is preferably 10°C or lower, more preferably 0°C or lower.

The copolyester of the present invention contains HO-(CH2)2n-OH(n
: Contains at least two types of diol component residues selected from 1 to 10), 40 to 99 mol% of aromatic dicarboxylic acid residues and 60 mol% of long chain aliphatic dicarboxylic acid residues based on the total acid components. It is preferable to contain up to 1 mol%.

Here, the alcohol component HO(CH2)
2n-OH (n: 1 to 10) refers to ethylene glycol, 1,4 butanediol, 1,6 hexanediol, 1
, 8-octanediol, etc., and preferably n is in the range of 1 to 4 in order to improve the mechanical properties and chemical resistance of the flexible film.

The copolymerized polyester in the present invention includes:
It is preferable to contain at least two of the above alcohol components. Here, in the present invention, each alcohol component is defined as being present when it is contained in an amount of 5 mol% or more.

[0020] If an attempt is made to configure the alcohol component into a one-component system, a problem arises in that the self-adhesiveness becomes too strong. In particular, it is preferable for one of the diol components to be 1,4-butanediol, since this provides good mechanical properties.

Although it is permissible to contain a small amount of branched glycol residues such as propylene glycol and neopentyl glycol, it is generally preferred to keep the content to less than 10 mol%, preferably less than 5 mol%. Similarly, an alcohol component containing an ether group such as diethylene glycol is also allowed to be included as a by-product component. It is usually in the range of about 0.01 to 4 mol%.

The copolyester of the present invention preferably contains aromatic dicarboxylic acid residues in an amount of 40 to 99 mol%.
Contains 60-1 mol% of long-chain aliphatic dicarboxylic acid residues. If the content of aromatic dicarboxylic acid residues is less than 40 mol%, the durability will be poor. On the other hand, if the aromatic dicarboxylic acid content exceeds 99 mol %, the sheet loses flexibility and becomes unsuitable as an interior sheet.

Here, the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6 naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid, diphenic acid, etc. Among these, terephthalic acid has the best durability and flexibility. This is preferable because it gives good results. Further, the long-chain aliphatic dicarboxylic acid is as described above.

The flexible film made of the copolymerized polyester of the present invention has a tensile Young's modulus of 0.1 to 50 kg/m.
m2, preferably 1
~30 kg/mm2. If the tensile Young's modulus is too small or too large, problems will occur in the winding property during the production of a flexible film, the suitability for processing into interior sheets, the suitability for stretching, and the like.

[0025] Furthermore, in the interior sheet of the present invention,
It is preferable to impart high durability, for example weather resistance. By imparting weather resistance, it is possible to prevent a decrease in flexibility and elongation of the interior sheet when used outdoors, for example. For this purpose, a UV absorber (for example, benzotriazole type: TINUVI manufactured by Nippon Ciba Geigy Co., Ltd.) is used.
N 234, CYASO manufactured by Nippon Cyanamid Co., Ltd.
It is effective to add RB UV5411, inorganic particles (zinc oxide, titanium oxide, iron oxide, etc.) within a range that does not impair the properties of the film. Addition is kneaded,
Either lamination or coating may be used. As the ultraviolet absorber, the above-mentioned benzotriazole-based and inorganic particle-based ultraviolet absorbers are preferred, but hydroquinone-based, salicylic acid-based, and benzophenone-based ultraviolet absorbers may also be used.

[0026] An antioxidant, an antistatic agent, and an inorganic filler may be added to the flexible polyester film used in the interior sheet of the present invention, if necessary. The addition of antioxidants can improve the chemical resistance (solvent resistance, etc.) of interior sheets, and the addition of antistatic agents can improve antistatic performance during interior sheet processing and use. By adding , it is possible to improve blocking resistance and infrared absorption and/or reflection.

[0027] As the above-mentioned antioxidant, phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, 4,4'-thiobis-(3-methyl-6-t-butylphenol) 2,2-di(4-hydroxyphenyl)propane, 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, octadecyl-3-(3,5-di- t-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetra-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,3,5-tris(4-t-
butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate; thiodipropionic acid esters such as di-n-dodecyl-thiodipropionate, di-n-octadecyl-thiodipropionate pionates, aliphatic sulfides and disulfides such as di-n-dodecyl sulfide, di-n-octadecyl sulfide, di-n-octadecyl disulfide; aliphatic, aromatic or aliphatic-aromatic phosphites and thiophosphites, such as: tri-n-dodecyl-phosphite, tris(n-nonylphenyl)phosphite, tri-n-dodecyl-trithiophosphite,
Examples include phenyl-di-n-nasyl phosphite and di-n-octadecyl-pentaerythritol diphosphite.

Examples of the antistatic agent include quaternary ammonium salts, amines, imidazolines, amine oxidized ethylene adducts, polyethylene glycols, and sorbitan esters.

[0029] Examples of the inorganic filler include silica, talc, calcium carbonate, etc., and these can be used alone or in combination of two or more. The blending amount is 5.0 per 100 parts by weight of polymer.
Up to 3.0 parts by weight, preferably 3.0 parts by weight or less.

The flexible polyester film of the present invention is
It is preferable that the film be substantially non-oriented in order to have good long-term dimensional stability. Here, "substantially non-oriented" means that the degree of orientation of molecular chains is sufficiently small that the anisotropy of mechanical properties and anisotropy of optical properties can be ignored, for example, in the longitudinal direction. The ratio of breaking strength in the width direction is in the range of 0.6 to 1.4, or the absolute value of the difference in refractive index (Nx, Ny, Nz) in the longitudinal direction, width direction, and thickness direction |Ni-Nj|(i ,j=x,y,z,i≠
j) is less than 0.1, preferably less than 0.05. If it has substantial orientation, it may deform if left for a long period of time, causing practical problems.

The flexible polyester film used in the interior sheet of the present invention preferably has a breaking elongation of 350% or more. If the elongation at break is smaller than this, there is a risk that when installing an interior sheet (for example, when pasting it on a wall or floor), problems may arise in that it is difficult to fit into corners and is likely to wrinkle. In addition, in the interior sheet of the present invention, as long as the elongation at break is sufficiently high, there is no need to make the breaking strength particularly high from the point of view of use, particularly for use in wallpaper or flooring.

[0032] Furthermore, the flexible polyester film used for the interior sheet of the present invention has a stress residual rate of 35%.
It is preferably within the range of ~70%. If the stress residual rate is smaller than this range, there is a risk that the interior sheet will loosen during construction, whereas if it is larger than this range, it will be likely to peel off after construction.

[0033] The interior sheet of the present invention can also use the above-mentioned flexible polyester film alone,
It can also be constructed as a laminate of the flexible film and sheets of other materials (for example, woven fabric, woven fabric, paper, plastic film, etc.).

In order to use the interior sheet of the present invention as an interior sheet for wallpaper or flooring, it may be subjected to printing, coloring, coating, graining, embossing, etc., as necessary.

Next, a method for manufacturing an interior sheet according to the present invention will be described, but the method is not limited thereto.

A. Production of copolymerized polyester Aromatic and/or alicyclic dicarboxylic acids constituting a predetermined hard segment, or dimethyl esters thereof, and a soft segment and a corresponding alcohol component are added, and a copolymerized polyester is produced by a well-known polyester polymerization method. get.

B. Manufacture of flexible polyester film for interior sheets After the copolymerized polyester thus obtained is dried, it is melt-extruded from an extruder, extruded in a sheet or cylindrical shape using a T-shaped nozzle or circular nozzle, and cooled. The extrusion temperature is usually from melting point +10 to melting point +
The temperature range is 80℃, and the cooling temperature is 5 to 90℃
The temperature is preferably in the range of 15 to 70°C.

Next, the cast film is heat treated, and the heat treatment temperature ranges from Tcc to the melting point (Tm) of the copolyester, preferably from Tcc to Tm.
The temperature range is -10°C. The treatment time is not particularly limited, but is usually from 1 second to 30 minutes.A particularly preferred method is to perform the heat treatment using a heated roll controlled at a predetermined temperature, in hot water, or in steam, as the treatment will be uniform and effective. This is preferable because it is accurate.

Next, after the heat treatment, the film is introduced into a drying roll or a drying oven as required, cooled to room temperature with a cooling roll, and subjected to surface treatment, etc., as required, and then wound up.

[0040] When the obtained flexible polyester film is used alone as an interior sheet, the film may be used as an interior sheet, and when it is used as a laminate with other material sheets, the laminate after lamination may be coated as necessary. , printed, colored, coated with paint, or grained or embossed,
To obtain an interior sheet according to the purpose.

(Method for Measuring Characteristics and Evaluating Effects) Next, methods for evaluating the characteristics and effects of the interior sheet of the present invention and the flexible film used therein will be explained.

(1) Mechanical properties Tensile Young's modulus and elongation at break conform to ASTM-D-8
82-81 (Method A). However, the measurement was performed at 25°C.

(2) Bromine number According to ASTM-D-1159. Unit is g/100g
It is expressed as

(3) Intrinsic viscosity (IV) Measured at 25°C using o-chlorophenol as a solvent. The unit is dl/g.

(4) Melting point (Tm), glass transition temperature (T
g), cold crystallization temperature (Tcc), ΔTcg, determined using a differential scanning calorimeter DSC2 (manufactured by PerkinElmer). The melt was maintained at 280° C. for 5 minutes under a nitrogen stream, and then cooled using liquid nitrogen. When the sample thus obtained is heated at a heating rate of 10° C./min, the change in specific heat due to the transition from the glass state to the rubber state is read and this temperature is defined as the glass transition temperature (Tg). Also,
The exothermic peak temperature accompanying crystallization is called the cold crystallization temperature (Tcc).
The endothermic peak temperature based on crystal melting was defined as the melting point (Tm). Further, ΔTcg is defined by the following formula. ΔTcg=Tcc-Tg

(5) Stress residual ratio film was sampled to a width of 10 mm, mounted on a tensile tester so that the sample length was 50 mm, and the tensile speed was set at 10 mm.
The stress F0 immediately after applying a tensile deformation of 25% of the sample length at 0 mm/min is measured, and then the stress F10 after holding this deformation amount for 10 minutes is measured and determined by the following equation. Stress residual rate = F10/F0 ×100 (%)

0047
]

[Example] Example 1 As acid components, dimethyl dimerate (manufactured by Unikema, bromine value 1 g/100 g) 10 mol%, adipic acid 5 mol%
and 85 mol% of terephthalic acid, 55 mol% of ethylene glycol and 45 mol% of 1,4-butanediol as alcohol components, and an intrinsic viscosity (IV) of 0.83.
A copolymerized polyester was polymerized. The obtained polymer was vacuum dried at 120°C by a conventional method, melted at 220°C with a 90mmφ extruder, and extruded into a sheet form from a T-die.
Electrostatic casting was carried out in a state where water was condensed on a cooling roll at 20°C. The obtained film was further heat-treated at 80° C. for 10 seconds to obtain a transparent film with a thickness of 100 μm.

A commercially available flame retardant paper containing aluminum hydroxide was bonded to this film using a polyurethane adhesive to prepare an interior sheet. Next, the interior sheet was attached to a gypsum board using an ethylene vinyl acetate copolymer resin adhesive. 4 gypsum board after pasting
After aging for two weeks at 0° C. and 90% RH, the surface film remained transparent and beautiful, and the attached sheet did not peel off. Table 1 shows the physical properties of the flexible polyester film used in this interior sheet.

Example 2 20 mol% of dimethyl dimerate and 80 mol% of terephthalic acid were used as acid components, and 40 mol% of ethylene glycol and 60 mol% of 1,4-butanediol were used as alcohol components, and the intrinsic viscosity (IV) A copolymerized polyester of 0.81 was polymerized. A transparent film with a thickness of 100 μm was prepared from the obtained polymer in the same manner as in Example 1, laminated with flame retardant paper, and then pasted on a gypsum board and subjected to an aging test. As in Example 1, there was no change in the surface layer of the film, and no peeling occurred at the attached portion. Table 1 shows the physical properties of the flexible polyester film used in this interior sheet.

Comparative Example 1 50 parts by weight of dioctyl phthalate (DOP: manufactured by Kyowa Hakko Kogyo Co., Ltd.) and 0 parts by weight of zinc stearate powder were added to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of about 1300.
．． 2 parts by weight and 10 parts by weight of epoxidized soybean oil were added and kneaded using rolls with a surface temperature of 160°C.
A μm press sheet was molded.

[0051] After laminating with flame retardant paper in the same manner as in Example 1, it was pasted onto a gypsum board and subjected to an aging test. After aging, the transparency of the vinyl chloride sheet decreased, and the surface became noticeably dirty, probably due to bleed-out of the plasticizer. Table 1 shows the physical properties of the vinyl chloride sheet used for this interior sheet.

Comparative Example 2 Dimethyl dimerate 5 mol % and terephthalic acid 95 mol % were used as acid components, ethylene glycol 100 mol % were used as alcohol components, and the intrinsic viscosity (IV) was 0.
．． 72 copolymerized polyesters were polymerized.

A transparent film with a thickness of 100 μm was prepared in the same manner as in Example 1, laminated with flame retardant paper, and then pasted on a gypsum board and subjected to an aging test. However, as in Example 1, although there was no change in the transparency of the surface film, peeling occurred at the corners of the attachment area. Table 1 shows the physical properties of the flexible polyester film used in this interior sheet.

[0054]

[Table 1]

[0055]

Effects of the Invention As described in detail above, when the interior sheet of the present invention is used, a flexible polyester film having the necessary flexibility and tensile Young's modulus as well as desired elongation and stress residual rate is used for interior decoration. It is possible to construct a sheet for Further, unlike conventional soft vinyl chloride sheets, the polyester film used in the interior sheet of the present invention does not have the problem of bleed-out because the polymer does not contain a plasticizer. Therefore, deterioration in quality and hygiene problems associated with bleed-out do not occur. Furthermore, by using the interior sheet of the present invention in place of the conventional vinyl chloride interior sheet, the mechanical properties as an interior sheet can be improved.
Not only can workability be improved, but also environmental problems during incineration can be eliminated, and the usable range can be greatly expanded.

Claims (4)

[Claims] Claim 1: Made of copolyester with a ΔTcg of 60°C or less, and a tensile Young's modulus of 0.1 to 50 kg.
An interior sheet characterized by using a flexible film of /mm2. Claim 2: The copolymerized polyester contains HO-(CH2)2n-OH (n: 1 to 10
) contains at least two types of diol component residues selected from
~99 mol%, 60-1 long chain aliphatic dicarboxylic acid residues
The interior sheet according to claim 1, wherein the interior sheet contains mol%. [Claim 3] The stress residual rate of the flexible film is 3.
Claim 1 wherein the elongation at break is 5% to 70% and 350% or more.
Or 2 interior seats. 4. The interior sheet according to claim 2 or 3, wherein the long-chain aliphatic dicarboxylic acid is a dimer acid.