JP2002129483A - Copolyester wallpaper - Google Patents

Abstract

(57) [Summary] [Problem] To provide a wallpaper having improved flame retardancy, traceability, calendering property, foaming property, and surface stain property [Solution] A polymer constituting a resin layer is a copolymerized polyester. The resin layer is composed of 100 parts by weight of the polymer and 30 to 500 parts by weight based on the polymer of a flame retardant-imparting inorganic compound. A polyester-based wallpaper comprising 1 to 50 parts by weight of a thermoplastic elastomer with respect to 100 parts by weight of a polymerized polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wallpaper obtained by adding a flame-retardant-imparting inorganic substance to a specific copolymerized polyester to have the flame retardancy required for a wallpaper and to have excellent calenderability.

[0002]

2. Description of the Related Art At present, a polyvinyl chloride wallpaper comprising a flexible polyvinyl chloride foam layer and a paper layer as a base material is widely used. Polyvinyl chloride wallpaper is suitable for wallpaper because the resin itself has good flame retardancy and good calenderability, but volatilization of plasticizers used for softening,
Attention has been paid to the generation of chlorine-based gas at the time of combustion, and in recent years the development of alternative wallpaper has been energetically made. As such a material, a wallpaper using a polyolefin-based resin has been developed, but the polyolefin resin is inherently easily burned, has poor calendering properties, and has poor foaming properties, so that it is finished in a voluminous product. In this case, the thickness of the resin layer must be increased, and the amount of heat generated during combustion increases.

[0003] Polyethylene terephthalate, which is a general polyester resin, is hard to burn as compared with polyolefin, but is inferior in calendering workability and foaming property, and thus is not suitable as a wallpaper. Also, as a wallpaper made of a copolymerized polyester, Japanese Patent Application No. 2000-123.
There is 512, but there is a problem that traces are left when the product is placed horizontally compared to general PVC wallpaper, and a plasticizer is used like a general PVC wallpaper to soften the resin layer. It is desirable not to use plasticizers to avoid indoor air pollution. In addition, Japanese Patent Application 2000-12
If the 3512 wallpaper is placed horizontally on a roll immediately after processing, it will leave a trace. Although this can be avoided by the storage method, it is inconvenient because it cannot be handled in the same way as the conventional polyvinyl chloride wallpaper.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a wallpaper made of a copolymerized polyester, which has good flame retardancy, calendering properties and foamability. Another object is to provide a trace-free wallpaper that is substantially free of plasticizer.

[0005]

According to the present invention, there is provided a polyester-based wallpaper characterized by adding 30 to 500 parts by weight of a flame retardant-imparting inorganic compound to 100 parts by weight of a copolymerized polyester as a resin layer. Further, it is a polyester-based wallpaper in which a thermoplastic elastomer is blended with a copolymer polyester which is a polymer constituting a resin layer, and the inconvenience of leaving traces is improved. Further, by using a copolymerized polyester having a glass transition point of 50 ° C. or lower, the wallpaper is substantially free of the need to add a plasticizer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. Copolyester The copolyester of the present invention is obtained by random copolymerization of two or more polyhydric carboxylic acids or polyhydric alcohols with one or both of a polyhydric carboxylic acid and a polyhydric alcohol. For this reason, the copolyester has low crystallinity. Copolymerized polyesters having a Tm of 200 ° C. or lower by the DSC method have calendering suitability, and more preferably amorphous polyesters having no Tm by the DSC method have good calendering suitability.

As the polyvalent carboxylic acids used in the production of such polyesters, aliphatic acids include adipic acid, glutaric acid, succinic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like. Examples of the alicyclic group include 1,4-cyclohexanedicarboxylic acid and cyclohexanediacetic acid. As aromatics, trivalent carboxylic acids such as terephthalic acid, orthophthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedimethylenecarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid, and pyromellitic acid And the like. However, the maximum amount of trivalent or higher carboxylic acid is about 0.5% mol. It is to be understood that the anhydrides, esters and acid chlorides corresponding to these acids are included. Among them, 1,4-cyclohexanedicarboxylic acid, which is a monomer having a ring structure and hard to rotate, is unfavorable and cannot be used in a large amount because the glass transition point is increased. Adipic acid or the like having an easily deformable methylene chain is preferable because the glass transition point is lowered and flexibility is imparted.

As a polyhydric alcohol, as an aliphatic,
Ethylene glycol, 1,2-propylene glycol,
1,4-butanediol, 1,5-pentanediol,
Neopentyl glycol, 1,6-hexanediol,
Examples include diethylene glycol, triethylene glycol, polyethylene glycol (up to a degree of polymerization of about 5), polytetramethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol, and the like. 3, 4 such as trimethylolpropane and pentaerythritol
There are also hydric alcohols. Examples of the alicyclic group include 1,4-cyclohexanedimethanol. Examples of the aromatic include bisphenol A. The trihydric or higher alcohol is desirably used in a maximum amount of about 0.5% mol from the viewpoint of moldability from the obtained polyester. this house,
1,4-cyclohexanedimethanol, which is a monomer having a ring structure and hard to rotate, is not preferable because it has a high glass transition point and cannot be used in a large amount. 1,6-hexanediol and the like having a methylene chain which is easy to be bent are preferable because the glass transition point is lowered and flexibility is imparted.

Particularly, a copolymerized polyester having a glass transition point of 20 ° C. or less is preferred because it is flexible and does not require a plasticizer, and is relatively hard to leave traces. Examples of the copolyester having a glass transition point of 50 ° C. or lower include Mitsubishi Rayon DC427 (glass transition point of 3 to 5 ° C.). As the copolyester having a glass transition point of more than 50 ° C, a copolymerized polyester having about 70% of ethylene glycol unit and about 30% of 1,4-cyclohexanedimethanol unit as alcohol PETG6763 manufactured by Eastman Chemical Co., Ltd. (glass transition point: 81 ° C) Can be mentioned.

In the present invention, the copolymerized polyester 10
To 0 parts by weight, 30 to 500 parts by weight of an inorganic compound is added. The inorganic compound is used in the form of a fine powder. As the inorganic compound, a metal compound having characteristics suitable for wallpaper, such that foaming properties do not deteriorate even when mixed well and mixed in a large amount, is preferable. Metal compounds are oxides, hydroxides, carbonates, (sulfites), silicates, and the like of metals such as aluminum, magnesium, calcium, zinc, titanium, iron, tin, and antimony.
Borate and the like. Particularly, calcium carbonate, aluminum hydroxide, and magnesium hydroxide are preferably used. If the amount is too small, the flame retardancy will be insufficient, and if it is too large, the calenderability will be poor. Particularly preferably 50 to 1
00 parts by weight.

In the present invention, a (meth) acrylic acid-based polymer may be blended in order to improve the foaming characteristics and further improve the calenderability. Specifically, a homopolymer of methyl (meth) acrylate or a polymerizable component of 50 to 95
% By weight of methyl (meth) acrylate, and examples of the copolymerization component include methacrylic acid esters of alcohols having 2 to 18 carbon atoms, acrylic acid esters of alcohols having 1 to 18 carbon atoms, styrene and α-methylstyrene. Aromatic vinyl, acrylonitrile, methacrylonitrile, etc.
Maleic acid, itaconic acid and the like can be mentioned. These copolymer components can be used alone or in combination of two or more. Further, it is particularly preferable that these (meth) acrylic acid polymers have a weight average molecular weight in the range of 500,000 to 5,000,000. Specific products include Metablen P, a product name sold by Mitsubishi Rayon Co., Ltd.
-501, 530, 531, 550, and 551.

In the present invention, a lubricant may be added in order to improve the calenderability. Conventionally known phosphate esters, fatty acid metal salts and the like can be used.
In particular, a mixture of a monofatty acid phosphate and a difatty acid phosphate is preferable as the phosphate. Examination of the properties of the mixture in combination with the lubricant used in the present invention as a lubricant revealed that a low-density oxidized polyethylene wax and a high-density oxidized polyethylene wax (acid value: 1 to 40 mgKOH / g) were used.
And a partially oxidized polyethylene having an average molecular weight of 10,000 or less) were confirmed to improve the effect as a lubricant. The amount of the polyethylene wax is preferably 0.01 to 5.0 parts by weight based on 100 parts by weight of the copolymerized polyester. Daikyo Kasei AX-518I (a mixture of monostearyl phosphate and distearyl phosphate 6: 4 and low-density oxidized and high-density oxidized polyethylene waxes. Acid number: 1 to 40 mgKOH / g and portion having an average molecular weight of 10,000 or less. Polyethylene oxide (mixture).

In the present invention, a plasticizer may be used to improve flexibility. However, if the molecular weight is high, the problem of volatilization can be almost eliminated, but the problem of migration and contamination remains. Therefore, it is desirable not to add a plasticizer. Since it is preferable that the plasticizer has good compatibility with the polymer, the SP (solubility parameter) value, which is an index to some extent, is preferably 8.7 or more, more preferably 9.0 or more. Specifically, those having a structure similar to the component constituting the polyester are preferable. Plasticizers for polyvinyl chloride such as phthalic acid esters, aliphatic dibasic acid esters, trimellitic acid esters, epoxidized oils, and adipic acid-based polyesters can be used. However, ethylene oxide (—CH ₂ ), which has not been conventionally used as a plasticizer for polyester resins, has been used.
Compounds having a polyalkylene oxide structure having —CH ₂ —O—) units and / or propylene oxide (—CH ₂ —CH (CH ₃ ) —O—) units are compatible with the copolyester and have plasticity Some agents are extremely effective. Ethylene oxide (-CH ₂ -
Preferred plasticizers having a CH ₂ —O—) unit include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and the like, and esters or ether compounds thereof. Similarly, propylene oxide (—CH ₂ —CH
Examples of those having a (CH ₃ ) —O—) unit include propylene glycol, dipropylene glycol, tripropylene glycol and the like, and esters or ethers thereof. In addition, ethylene oxide (-C
Polyalkylene glycol compounds composed of H ₂ —CH ₂ —O—) units and propylene oxide (—CH ₂ —CH (CH ₃ ) —O—) units, and also composed of blocks of polyethylene oxide and polypropylene oxide are also provided. Naturally, it is useful as a plasticizer constituting the polyester composition of the present invention. Ethylene oxide adduct of poly (propylene oxide) glycol,
A copolymer of ethylene oxide and propylene oxide can be mentioned as a substance having both structures.
Ether compounds include alkylphenol ethylene oxide nmol adducts and higher alcohol ethylene oxide nmol adducts, and ester compounds include fatty acid ethylene oxide nmol adducts and aliphatic dibasic acid ester ethylene oxide nmol adducts. There is.
Other compounds having the above-mentioned units include an ethylene oxide nmol adduct of a higher fatty acid amine, an ethylene oxide nmol adduct of a fatty acid amide, and a bisphenol A ethylene oxide nmol adduct. Specific examples include Asahi Denka Kogyo Co., Ltd. RS-1000 (polyetherester). Fatty acid glycerin esters are also compatible with the copolyester and are extremely effective as plasticizers. Fatty acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, tetracosanoic acid, undecanoic acid, oleic acid, Elaidic acid,
Examples include petroseric acid, erucic acid, linoleic acid, and linoleic acid. Among these single or plural fatty acid mono-, di-, triglycerides and acetylated glycerides, diacetylated monofatty acid glycerides are particularly preferably used. Specifically, Riken Vitamin PL-01
2G (glycerin diacetomonolaurate).

In the present invention, the copolymerized polyester 10
It is preferable to add 1 to 50 parts by weight of the thermoplastic elastomer to 0 parts by weight to prevent traces. Examples of the thermoplastic elastomer include styrene, polyolefin, polyurethane, polyamide, polyvinyl chloride, polyester, and fluoro rubber.
Of these, styrene is preferred from the viewpoint of compatibility with the copolyester and flexibility, and particularly, by adding 1 to 20 parts by weight of SIS (polystyrene-polyisoprene-polystyrene thermoplastic elastomer), traceability and flexibility are good. Becomes Specifically, Shell Japan D-111
7 (SIS).

In the present invention, it is preferable to foam. Examples of the foaming agent for the resin composition forming the foamable copolymerized polyester layer include ADCA (azodicarbonamide), OBSH (P, P'-oxybis (benzenesulfonylhydrazide)), and TSH (paratoluenesulfonylhydrazide). ) Chemical blowing agents such as DPT (dinitropentamethylenetetramine) or a blend of these blowing agents are preferred. ADCA is # 3170 (Otsuka Chemical Co., Ltd.). The foaming agent can produce a foamable decorative sheet having good foaming characteristics by combining with the copolymerized polyester resin composition. 0.5 to 5 parts by weight of a foaming aid (kicker) such as urea-based, organic acid-based, or metal salt-based, such as zinc oxide or zinc stearate, depending on the softening temperature of the copolymerized polyester used. Thereby, the foaming property is improved by lowering the decomposition start temperature of the foaming agent. The expansion ratio is preferably 2 to 20 times,
More preferably, it is 5 to 20 times. JIS for wallpaper
In order to improve the flame retardancy characteristic indicated by the temperature time area (corresponding to tdθ) exceeding the standard temperature curve defined in A1321, it is important to make the flame resistance as light as possible. For this reason, it is advantageous to use a foamed structure in order to reduce the weight while maintaining the required thickness in appearance. Therefore, a good foaming property is required for the material for making the wallpaper, and the foaming ratio is at least 2 times or more. It is necessary to have a foaming ratio of at least 5 times or more in order to give a sense of volume. However, if the magnification is set to 20 times or more, the cell roughness is severe at present and the commercial value cannot be sufficiently satisfied.

The wallpaper of the present invention can be processed by a calendering method, and a film having a thickness of about 0.1 to 1.0 mm can be produced. The appropriate temperature range of the calender is 100 to 220 ° C, preferably 120 to 200 ° C. Wallpaper having a base material layer can be produced by laminating the paper for wallpaper base material under heat and pressure. More decorative,
Processing such as matting can be performed. For example, for printing (pattern printing) as a means of decoration, a method of printing with a printing ink using an acrylic resin-based and / or urethane resin-based vehicle with an engraving roll of a gravure printing machine and drying in a drying oven is employed. be able to.
In addition, for the surface treatment such as the matting treatment, a method of applying a gloss adjusting agent by the same printing means as described above can be adopted. The acrylic resin-based and / or urethane resin-based treating agent can be employed as a vehicle for the treating agent. The wallpaper of the present invention is also preferable in that it has good affinity for inks and processing agents. Further, the wallpaper of the present invention has good squeezing transferability.

[0017]

EXAMPLES Examples 1 to 9 and Comparative Example 1 As shown in Table 1, polyester resin compositions for calender molding were prepared. The calendering processability was evaluated using a test roll. Test roll conditions are roll temperature 150
° C, rotation speed 30/25 (times / min), roll gap (m
m), ○ indicates that there was no problem in both the bank state (× if there is rough skin) and the state of the sheet ears (sawtooth = ×), and Δ indicates that there was a slight problem. A sheet having the composition shown in Table 1 having a thickness of 0.12 mm was prepared using a calender and 65 g
/ M ² Laminated with plain paper for wallpaper, normal pattern printing is performed in the printing process, and the thickness is 0.8 m by normal foaming and drawing.
m wall paper products were manufactured and wound into 50 m and stacked in three layers. The traces were clearly marked by visual observation = x, clearly seen = =, none = =. Foamability was determined by visual observation of the surface condition of the product: surface roughness or insufficient foaming = ×, slight surface roughness or insufficient foaming = △, good = ○. Flame retardancy is JI
The test was performed according to SA1321-1975, and it was evaluated as “Flame retardant class 2 passed = ○” and “Flame retardant class 2 failed = ×”.

[0018]

[Table 1]

[0019]

As described above, the present invention has good calendering properties, and has good flame retardancy and foaming properties in wallpaper.
The surface dirt is improved, and the excellent effect of providing a wallpaper with no trace is brought about.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D21H 27/20 D21H 27/20 A // B32B 27/36 B32B 27/36 (C08L 67/00 (C08L 67 / 00 101: 00) 101: 00) (72) Inventor Masao Sasaki 1F Kobe, Yoshida-cho, Haibara-gun, Haibara-gun, Shizuoka Prefecture F-term (reference) 4F055 AA17 BA11 BA12 CA05 CA11 DA10 FA24 FA40 GA20 GA26 GA34 4F100 AA01A AA08A AA18A AA19A AK41A AL01A AL05A AL09A AT00B BA02 BA07 CA08A GB08 JA05A JB16A JJ07 YY00A 4J002 BP012 CF031 CF041 CF051 CF081 DE076 DE086 DE096 DE106 DE116 DE126 DE136 A18 DG DG DG DG DG 016 DG DG 020 EA40 FA30 GA23

Claims (4)

[Claims] 1. A resin constituting a resin layer is a copolymerized polyester, and the resin layer is composed of 100 parts by weight of the polymer and 30 to 500 parts by weight of the flame-retardant inorganic compound with respect to the polymer. Polyester wallpaper. 2. The polyester-based wallpaper according to claim 1, wherein the polymer constituting the resin layer is obtained by blending 1 to 50 parts by weight of a thermoplastic elastomer with respect to 100 parts by weight of the copolymerized polyester. 3. The copolymerized polyester has a glass transition point of 50.
C. or lower, and the resin layer contains substantially no plasticizer. 4. The wallpaper according to claim 1, wherein the flame-retardant-providing inorganic compound is a single or a mixture selected from calcium carbonate, aluminum hydroxide and magnesium hydroxide.