JP3128850B2 - Interior sheet - Google Patents

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 copolymerized polyester film.

[0002]

2. Description of the Related Art As an interior sheet used for wallpaper or flooring material, conventionally, a soft vinyl chloride resin sheet or a laminate of such a sheet with paper, cloth, another resin film, etc. has been colored,
Those subjected to printing, coating (for surface protection, static electricity prevention, etc.), and those subjected to graining, embossing, and the like are frequently used. This interior seat
Along with the flexibility enough to follow the shape of the wall or floor, it has a breaking elongation that does not easily break and does not easily wrinkle even when it is stretched because it is attached to the corner of the wall or floor. Required. In addition, it is often required to maintain an appropriate stress that does not loosen or peel off after construction.

[0003]

However, the conventional interior sheet using a soft vinyl chloride sheet has the following problems.

[0004] First, in the case of soft vinyl chloride, the plasticizer migrates to the surface over time (bleed-out), so that the bleed-out plasticizer itself deteriorates the surface quality or causes a hygiene problem. There is a risk. In addition, since the bleed-out plasticizer forms an adhesive surface layer, dust adheres to the surface layer, which may cause deterioration in quality and hygienic problems.

[0005] Further, since vinyl chloride is not so high in chemical resistance, dirt cannot be removed with an organic solvent, causing problems such as complicating the cleaning process when processing and using an interior sheet.

Further, since vinyl chloride contains a halogen element, toxic gas is generated when incinerated. for that reason,
The treatment of the used interior sheet is restricted, and as a result, the use of a large amount of the soft vinyl chloride sheet as the interior sheet is also restricted due to environmental problems.

[0007] To solve the above problem, there are some using polyvinyl fluoride or the like from the viewpoint of flame retardancy, but the cost is high,
Not suitable for general purpose use or mass use.

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

[0009]

According to the present invention, there is provided an interior sheet comprising a copolyester having a ΔTcg of 60 ° C. or less and a tensile Young's modulus of 0.1 to 50 kg / mm ^2.
Product of flexible polyester film and other material sheets
Consists of layers.

The copolymerized polyester constituting the flexible polyester film of the present invention has a cold crystallization temperature (Tcc).
And difference from glass transition temperature (Tg) (Tcc-Tg)
Is required to be 60 ° C. or lower, preferably 50 ° C. or lower. If ΔTcg is too large, the tensile Young's modulus may increase over time,
Problems such as deterioration in flexibility occur.

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, dodecandionic acid, and dimer acid are used.
[CH ₂ ] _n- COOH is preferably an aliphatic polyester composed of an aliphatic dicarboxylic acid and an aliphatic and / or alicyclic diol. Particularly, the soft segment contains a long-chain aliphatic dicarboxylic acid. Is preferable in terms of improving flexibility and elongation at break.

In the present invention, the long-chain aliphatic dicarboxylic acid is a dicarboxylic acid having an alkylene group having 8 to 60 carbon atoms, such as sebacic acid, eicoic acid, dodecandioic acid and dimer acid. The range of from 50 to 50 is preferable because the flexibility becomes good.

Particularly, in the present invention, among the long-chain aliphatic dicarboxylic acids, a long-chain branched aliphatic dicarboxylic acid having a branched structure is preferable, and among them, the use of dimer acid is preferred for flexibility and elongation at break. It is preferable for improving the degree. Here, the dimer acid is a mixture of a linear branched structure and a cyclic branched structure obtained by dimerizing an unsaturated aliphatic carboxylic acid methyl ester such as methyl oleate, and usually has an unsaturated bond in the molecule. However, those obtained by hydrogenation and having a bromine value of 0.05 to 10 g / 100 g, preferably 0.1 to 5 g / 100 g are preferable because of excellent flexibility and elongation at break.

[0014] The hard segment of the above-mentioned copolymerized polyester has a melting point of 20 when the polymer is constituted alone.
0 ° C or higher, glass transition temperature of 90 ° C or lower, ΔTcg of 8
The temperature is preferably 0 ° C. or lower in order to improve the chemical resistance, solvent resistance, and the like. It is preferable to be composed of at least one selected from aromatic and / or alicyclic ester units such as dicarboxylate. In particular, those having a terephthalic acid residue are preferable because durability is improved.

Here, the intrinsic viscosity of the copolyester preferably used is 0.5 to 2.0 dl / g,
Preferably, it is 0.7 to 1.8 dl / g. By setting the intrinsic viscosity in such a range, both the film forming property and the mechanical properties of the polyester film are improved.

Further, the melting point (T
m) is practically preferably from 130 to 250 ° C., and more preferably from 140 to 230 ° C.
Further, the glass transition temperature (Tg) is preferably 10 ° C. or lower, more preferably 0 ° C. or lower.

In the present invention, the copolymerized polyester is HO- (CH ₂ ) _2n -OH (n: 1) as an alcohol component.
10 to 10), at least 40 to 99% by mole of aromatic dicarboxylic acid residues and 6 to 6% of long-chain aliphatic dicarboxylic acid residues based on the total acid components.
It is preferable to contain 0-1 mol%.

Here, the alcohol component HO (CH ₂ ) _2n
-OH (n: 1 to 10) means ethylene glycol,
1,4 butanediol, 1,6 hexanediol, 1,
It is an aliphatic diol component such as 8-octanediol. 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, it is defined that each alcohol component is present when the content is 5 mol% or more.

If the alcohol component is composed of a one-component system, there is a problem that the self-adhesiveness becomes too strong. In particular, it is preferable that one of the diol components is 1,4-butanediol because the mechanical properties are improved.

Although it is permissible to contain a small amount of a branched glycol residue such as propylene glycol or neopentyl glycol, it is usually preferable to keep the amount to less than 10 mol%, preferably less than 5 mol%. Similarly, an alcohol component containing an ether group such as diethylene glycol is allowed to be contained as a by-product. Usually, it is in the range of about 0.01 to 4 mol%.

The copolymerized polyester of the present invention preferably contains 40 to 99 mol% of aromatic dicarboxylic acid residues,
Long-chain aliphatic dicarboxylic acid residues are contained in an amount of 60 to 1 mol%. When the amount of the aromatic dicarboxylic acid residue is less than 40 mol%, the durability becomes poor. On the other hand, if the amount of the aromatic dicarboxylic acid exceeds 99 mol%, the flexibility is lost and the sheet becomes unsuitable as an interior sheet.

Here, the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5 sodium sulfoisophthalic acid, diphenic acid, etc. Among them, terephthalic acid has both durability and flexibility. It is preferable because it becomes good. The long-chain aliphatic dicarboxylic acid is as described above.

The flexible film comprising the copolymerized polyester of the present invention has a tensile Young's modulus of 0.1 to 50 kg / mm ^2.
It is necessary to be in the range of, preferably, 1 to 30
kg / mm ² . If the tensile Young's modulus is too small or too large, problems arise in the winding property at the time of forming a flexible film, and the suitability at the time of processing into an interior sheet and at the time of stretching.

In the interior sheet of the present invention,
It is preferable to impart high durability, for example, weather resistance. By imparting the weather resistance, for example, when used outdoors, the flexibility and elongation of the interior sheet can be prevented from lowering. For that purpose, an ultraviolet absorber (for example, benzotriazole type: TINUVI manufactured by Nippon Ciba Geigy Co., Ltd.)
N234, Nippon Cyanamid Co., Ltd. CYASOR
B UV5411, inorganic particles: zinc oxide, titanium oxide, iron oxide, etc.) is effective within a range that does not impair the properties of the film. The addition may be kneading, laminating, or coating. As the ultraviolet absorber, the above-mentioned benzotriazole-based and inorganic particle-based are preferable, but a hydroquinone-based, salicylic acid-based, and benzophenone-based ultraviolet absorber may be used.

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

Examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol and 4,4'-thiobis- (3-methyl-6-t-butylphenol). 2,2-di (4-hydroxyphenyl)
Propane, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, octadecyl-3- (3,5-di-tert-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-tert-butyl-4-hydroxybenzyl) isocyanurate; thiodipropionate such as di-n-dodecyl -Thiodipropionate, di-n-octadecyl-thiodipropionate, 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, phenyl-di-n-nacilphosphite, di-n-
Octadecyl-pentaerythritol diphosphite and the like can be mentioned.

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

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

The flexible polyester film of the present invention comprises:
It is preferable to use a substantially non-oriented film in order to improve the long-term dimensional stability. Here, being substantially non-oriented means that the degree of molecular chain orientation is sufficiently small and the anisotropy of mechanical properties and anisotropy of optical properties are at a level that can be neglected sufficiently. The absolute value of the difference in refractive index (Nx, Ny, Nz) | Ni−Nj | (i) in the range of the breaking strength in the width direction of 0.6 to 1.4 or in the longitudinal direction, the width direction, and the thickness direction. , J = x, y, z, i ≠
j) is less than 0.1, preferably less than 0.05. When it has a substantial orientation, it may be deformed when left for a long period of time and cause a practical problem.

The flexible polyester film used for the interior sheet of the present invention preferably has an elongation at break of 350% or more. If the elongation at break is smaller than this, when constructing an interior sheet (for example, when attaching it to a wall or floor),
There is a possibility that a problem that it is difficult to fit the corner and that it is easily wrinkled may occur. In the interior sheet of the present invention,
If the breaking elongation is sufficiently high, the breaking strength does not need to be particularly high from the viewpoint of applications, particularly from the viewpoint of applications used for wallpaper and flooring materials.

The flexible polyester film used for the interior sheet of the present invention has a residual stress ratio of 35%.
It is preferably within the range of 70%. If the stress residual ratio is smaller than this range, loosening may occur at the time of application of the interior sheet. Conversely, if it is larger than this range, the sheet tends to peel off after application.

The interior sheet of the present invention, such as flexibility polyester film and another material strip (e.g. woven, nonwoven fabric, paper, plastic film, etc.) described above are constructed as a laminate of.

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, or the like, as necessary.

Next, a method for producing the interior sheet of the present invention will be described, but it is needless to say that the present invention is not limited to this.

A. Production of Copolyester Aromatic and / or alicyclic dicarboxylic acid constituting a predetermined hard segment or a dimethyl ester composed of these and a soft segment and an alcohol component corresponding thereto are added, and the copolyester is prepared by a well-known polyester polymerization method. Get.

B. Manufacture of flexible polyester film for interior sheet After drying the copolymer polyester thus obtained, it is melt-extruded from an extruder and discharged from the die into a sheet or cylinder using a T-type die or circular die, and cooled. The sheet or the cylinder thus obtained is solidified by being introduced into a roll or a cooling medium such as water (the sheet or cylinder thus obtained is hereinafter referred to as a cast film).
The temperature range is 80 ° C, and the cooling temperature is 5 to 90 ° C.
, Preferably in the range of 15 to 70 ° C.

Next, the cast film is subjected to a heat treatment. The heat treatment temperature ranges from Tcc to the melting point (Tm) of the copolymerized polyester, preferably from Tcc to Tm.
The temperature range is −10 ° C. Although the treatment time is not particularly limited, it is usually 1 second to 30 minutes, and a particularly preferable method is that the heat treatment is performed uniformly in a heating roll controlled at a predetermined temperature, in hot water, or in steam. It is preferable because it is a target.

Next, after the heat treatment, the film is guided to a drying roll or a drying oven as needed, cooled to a room temperature by a cooling roll, and subjected to a surface treatment or the like, if necessary, and wound up.

The obtained flexible polyester film is
Although it is configured as a laminate with other material sheets , the laminate after lamination is subjected to printing, coloring, coating of coating liquid, or graining or embossing as necessary, for interior use according to the application Get a sheet.

(Method for Measuring Characteristics and Method for 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 described.

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

(2) Bromine value According to ASTM-D-1159. The unit is g / 100g
Expressed by

(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 (Tm)
g), cold crystallization temperature (Tcc), ΔTcg Determined using a differential scanning calorimeter DSC2 (manufactured by PerkinElmer). The mixture was melted and maintained at 280 ° C. for 5 minutes under a nitrogen stream, and then cooled using liquid nitrogen. When the sample thus obtained was heated at a rate of 10 ° C./min, the specific heat change based on the transition from the glassy state to the rubbery state was read, and this temperature was taken as the glass transition temperature (Tg). The exothermic peak temperature accompanying crystallization was defined as a cold crystallization temperature (Tcc), and the endothermic peak temperature based on crystal melting was defined as a melting point (Tm). ΔTcg is defined by the following equation. ΔTcg = Tcc−Tg

(5) Residual stress ratio The film was sampled to a width of 10 mm, mounted on a tensile tester so that the test length became 50 mm, and the tensile speed was 100 mm.
/ Min, the stress F ₀ immediately after the tensile deformation of 25% of the test length is given, and then the stress F ₁₀ after holding the deformation for 10 minutes while maintaining the amount of deformation. Stress residual rate _{= F 10 / F 0 × 100} (%)

[0047]

Example 1 10 mol% of dimethyl dimerate (manufactured by Unichema, bromine number 1 g / 100 g) and 5 mol% of adipic acid as acid components
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 0.8.
The copolymerized polyester of No. 3 was polymerized. The obtained polymer was vacuum-dried at 120 ° C. by a conventional method, melted at 220 ° C. with a 90 mmφ extruder, extruded into a sheet from a T-die,
In a state where water was condensed on a cooling roll at 20 ° C., electrostatic application casting was performed. The obtained film was further subjected to a heat treatment at 80 ° C. for 10 seconds to obtain a transparent film having a thickness of 100 μm.

A commercially available flame-retardant paper containing aluminum hydroxide was bonded to this film with a polyurethane adhesive to prepare an interior sheet. Next, the interior sheet was attached to a gypsum board with an ethylene vinyl acetate copolymer resin adhesive. 4 gypsum boards after pasting
The film was aged at 0 ° C. and 90% RH for 2 weeks, but the surface film remained transparent and remained beautiful, and the attached sheet did not peel off. Table 1 shows the physical properties of the flexible polyester film used for the interior sheet.

Example 2 20 mol% of dimethyl dimer and 80 mol% of terephthalic acid were used as the acid component, and 40 mol% of ethylene glycol and 60 mol% of 1,4-butanediol were used as the alcohol component. 0.81 copolymerized polyester was polymerized. From the obtained polymer, a transparent film having a thickness of 100 μm was prepared in the same manner as in Example 1, laminated with flame-retardant paper, and then applied to a gypsum board to perform an aging test. As in the case of Example 1, there was no change in the surface film, and no peeling or the like occurred in the affixed portion. Table 1 shows the physical properties of the flexible polyester film used for the interior sheet.

Comparative Example 1 50 parts by weight of dioctyl phthalate (DOP: manufactured by Kyowa Hakko Kogyo Co., Ltd.), 0.2 parts by weight of zinc stearate powder, and epoxidation were added to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of about 1300. Add 10 parts by weight of soybean oil,
Kneading with a roll having a surface temperature of 160 ° C.
A 0 μm press sheet was formed.

After laminating with flame-retardant paper in the same manner as in Example 1, it was pasted on a gypsum board and subjected to an aging test. The transparency of the vinyl chloride sheet after aging was lowered, and the stain on the surface, which was considered to be caused by bleed out of the plasticizer, became remarkable. Table 1 shows the physical properties of the vinyl chloride sheet used for the interior sheet.

COMPARATIVE EXAMPLE 2 5 mol% of dimethyl dimer and 95 mol% of terephthalic acid were used as an acid component, and 100 mol% of ethylene glycol was used as an alcohol component.
0.72 copolymerized polyester was polymerized.

A transparent film having a thickness of 100 μm was prepared in the same manner as in Example 1, laminated with flame-retardant paper, and then stuck on a gypsum board to perform an aging test. However, as in Example 1, although the transparency of the film on the surface layer did not change, peeling occurred at the corner of the sticking portion.
Table 1 shows the physical properties of the flexible polyester film used for the interior sheet.

[0054]

[Table 1]

[0055]

As described in detail above, when using the interior sheet of the present invention, the interior sheet is formed using a flexible polyester film having the required elongation and stress retention while having the necessary flexibility and tensile Young's modulus. Sheet can be configured. Further, the polyester film used for the interior sheet of the present invention does not have a bleed-out problem because the polymer does not contain a plasticizer, unlike a conventional soft vinyl chloride sheet. Therefore, there is no problem of quality deterioration and hygiene caused by bleed-out. Furthermore, by using the interior sheet of the present invention instead of the conventional vinyl chloride interior sheet, mechanical properties as an interior sheet,
Not only the workability can be improved, but also environmental problems at the time of incineration can be eliminated, and the usable range can be greatly expanded.

────────────────────────────────────────────────── (5) References JP-A-3-263435 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 27/28 C08G 63/181 C08J 5 / 18 C08L 67/00 E04F 13/18

Claims (4)

(57) [Claims] 1. Lamination of a flexible polyester film comprising a copolyester having a ΔTcg of 60 ° C. or less and a tensile Young's modulus of 0.1 to 50 kg / mm ² and a sheet of another material
An interior sheet comprising a body . 2. The copolymerized polyester contains at least two diol component residues selected from HO— (CH ₂ ) _2n —OH (n: 1 to 10) as an alcohol component,
An aromatic dicarboxylic acid residue is added in an amount of 40 to 99 with respect to the total acid component.
Mol%, long chain aliphatic dicarboxylic acid residue of 60 to 1 mol%
The interior sheet according to claim 1, wherein 3. The flexible film has a residual stress ratio of 35.
The interior sheet according to claim 1 or 2, wherein the elongation at break is 350% or more. 4. The interior sheet according to claim 2, wherein the long-chain aliphatic dicarboxylic acid is a dimer acid.