JP2001164499A - Wall paper - Google Patents

Abstract

(57) [Problem] To provide an inexpensive wallpaper that has good chemical resistance and gas barrier properties, has excellent barrier properties for volatile organic compounds, and is inexpensive. SOLUTION: [1] A wallpaper using a film made of a liquid crystalline polymer that exhibits optical anisotropy when melted. [2] Wallpaper made of a film made of a liquid crystalline polymer exhibiting optical anisotropy when melted, and a laminated film made of a thermoplastic resin (excluding the liquid crystalline polymer) and / or paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to wallpaper used for building interiors, which has good chemical resistance and gas barrier properties, and has excellent barrier properties for volatile organic compounds.

[0002]

2. Description of the Related Art In recent years, plastic films such as polyvinyl chloride and ethylene-vinyl alcohol copolymer have conventionally been used as wallpaper for building interiors, but they do not always sufficiently satisfy the demands from the market. is the current situation. For example, a wallpaper made of a polyvinyl chloride film has a poor barrier property of volatile organic compounds generated from an internal building material covered by the wallpaper, so that the volatile organic compound permeates the wallpaper and enters a room. Causing sick house symptoms, poor chemical resistance, making it difficult to clean even if the wallpaper is contaminated, bleeding of components in the polyvinyl chloride plasticizer, etc. Has been pointed out by the market as a problem. In addition, generation of chlorine-based gas at the time of incineration after use has also been regarded as a problem. Wallpaper made of a film of an ethylene-vinyl alcohol copolymer has been widely used, but the barrier properties and chemical resistance of volatile organic compounds were insufficient depending on the use.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an inexpensive wallpaper which has good chemical resistance and gas barrier properties, has excellent barrier properties for volatile organic compounds, and is inexpensive.

[0004]

Means for Solving the Problems The present inventors have intensively studied to solve such a problem, and as a result, when a film made of a liquid crystalline polymer exhibiting optical anisotropy when melted is used for wallpaper. Finds that the above problem can be solved,
The present invention has been reached. That is, the present invention relates to a wallpaper using a film made of a liquid crystalline polymer exhibiting optical anisotropy when melted. Further, the present invention, a film comprising a liquid crystal polymer showing optical anisotropy when melted,
The present invention relates to a wallpaper using a laminated film made of a film made of a thermoplastic resin (excluding a liquid crystalline polymer) and / or paper.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Examples of the liquid crystalline polymer that exhibits optical anisotropy when melted include, for example, wholly aromatic polyesters, polyimides, polyesteramides, and the like, and resin compositions containing them. In the present invention, the liquid crystalline polymer is preferably a composition containing a liquid crystalline polyester or a liquid crystalline polyester. From the viewpoint of moldability and the performance of the obtained film, (A) the liquid crystalline polyester is continuously used in the present invention. It is more preferable to use a liquid crystal polyester resin composition in which (B) a copolymer having a functional group reactive with liquid crystal polyester is used as a dispersed phase.

[0006] The liquid crystal polyester referred to here is a polyester called a thermotropic liquid crystal polymer.
Specifically, (1) a compound comprising a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. (2) Those comprising a combination of different aromatic hydroxycarboxylic acids. (3) Those comprising a combination of an aromatic dicarboxylic acid and a nucleus-substituted aromatic diol. (4) Those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate. And those which form an anisotropic melt at a temperature of 400 ° C. or lower are preferred. In addition, in place of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, ester-forming derivatives thereof may be used.

The repeating structural units of the liquid crystal polyester include the following repeating structural units derived from an aromatic dicarboxylic acid, the following repeating structural units derived from an aromatic diol,
Examples of the repeating structural unit derived from an aromatic hydroxycarboxylic acid include, but are not limited to, these.

A repeating structural unit derived from an aromatic dicarboxylic acid:

[0009]

A repeating structural unit derived from an aromatic diol:

[0011]

A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

A liquid crystal polyester which is particularly preferable from the balance of heat resistance, mechanical properties and workability is And more preferably at least 30 mol% of the entire repeating unit.
The above is included. Specifically, the combination of repeating structural units is preferably any one of the following (I) to (VI).

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

The production methods of the liquid crystal polyesters (I) to (VI) are described, for example, in JP-B-47-47870, JP-B-63-3888, JP-B-63-3891, and JP-B-56-18016. JP-A-2-515
No. 23, and the like. Of these, a combination of (I), (II) or (IV) is preferable, and a combination of (I) or (II) is more preferable.

In the field where high heat resistance is required in the liquid crystal polyester resin composition of the present invention, the liquid crystal polyester of the component (A) contains 30 to 80 mol% of the following repeating unit (a '), A liquid crystal polyester in which (b ') is 0 to 10 mol%, the repeating unit (c') is 10 to 25 mol%, and the repeating unit (d ') is 10 to 35 mol% is preferably used.

[0022] (In the formula, Ar is a divalent aromatic group.)

The component (B) used in the liquid crystal polyester resin composition of the present invention is a copolymer having a functional group reactive with the liquid crystal polyester. The functional group reactive with the liquid crystal polyester may be any functional group having reactivity with the liquid crystal polyester, and specific examples include an oxazolyl group, an epoxy group, and an amino group.
Preferably, it is an epoxy group. The epoxy group or the like may be present as a part of another functional group, and such an example includes a glycidyl group.

In the copolymer (B), the method for introducing such a functional group into the copolymer is not particularly limited, and it can be carried out by a known method. For example, at the stage of synthesizing the copolymer, it is possible to introduce the monomer having the functional group by copolymerization, or it is also possible to graft copolymerize the monomer having the functional group to the copolymer. It is.

As the monomer having a functional group reactive with the liquid crystal polyester, particularly, the monomer containing a glycidyl group, unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether is preferably used.

The unsaturated carboxylic acid glycidyl ester is
Preferably a general formula Wherein R is a hydrocarbon group having an ethylenically unsaturated bond and having 2 to 13 carbon atoms. The unsaturated glycidyl ether is preferably a compound represented by the general formula: (R ′ has 2 to 18 carbon atoms having an ethylenically unsaturated bond.
A hydrocarbon group, X is -CH ₂ -O- or It is. ).

Specifically, the unsaturated carboxylic acid glycidyl ester includes, for example, glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconate, triglycidyl butenetricarboxylate,
Glycidyl p-styrenecarboxylate and the like can be mentioned. As unsaturated glycidyl ethers,
For example, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, styrene-p-glycidyl ether and the like are exemplified.

The copolymer (B) having a functional group reactive with the liquid crystal polyester preferably contains 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. It is a copolymer containing.

The copolymer (B) having a functional group reactive with the liquid crystal polyester may be a thermoplastic resin or a rubber, or a mixture of a thermoplastic resin and a rubber. You may. A rubber having excellent thermal stability and flexibility of a molded product such as a film or sheet obtained by using the liquid crystal polyester resin composition is more preferable.

More preferably, the copolymer (B) having a functional group reactive with the liquid crystal polyester is
A copolymer having a heat of fusion of crystal of less than 3 J / g. The copolymer (B) preferably has a Mooney viscosity of 3 to 70, more preferably 3 to 30 and more preferably 4 to 30.
25 are particularly preferred. The Mooney viscosity here refers to a value measured using a large rotor at 100 ° C. according to JIS K6300. Outside these ranges, the thermal stability and flexibility of the composition may be undesirably reduced.

The rubber mentioned here corresponds to a polymer substance having rubber elasticity at room temperature according to a new edition of Polymer Dictionary (edited by the Society of Polymer Science, published in 1988, Asakura Shoten).
Specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (including random copolymer, block copolymer (including SEBS rubber or SBS rubber, etc.), and graft copolymer). The hydrogenated product, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber, isobutylene-isoprene copolymer, acrylate-ethylene copolymer rubber , Ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene-propylene-styrene copolymer rubber, styrene-
Isoprene copolymer rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluoro rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-non-conjugated diene copolymer rubber, Examples include thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (eg, polypropylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and the like. Among them, acrylate-ethylene copolymers are preferably used, and (meth) acrylate-
Ethylene copolymer rubber is more preferred.

These rubber-like substances are produced by any production method (eg, emulsion polymerization method, solution polymerization method, etc.) and any catalyst (eg, peroxide, trialkylaluminum, lithium halide, nickel-based catalyst, etc.). It may be something.

In the present invention, the rubber as the copolymer (B) is a rubber having a functional group reactive with the liquid crystal polyester among the above rubbers. In the rubber, a method for introducing a functional group reactive with the liquid crystal polyester into the rubber is not particularly limited, and can be performed by a known method.
For example, it is possible to introduce the monomer having the functional group by copolymerization at the stage of synthesizing the rubber, or it is also possible to graft copolymerize the monomer having the functional group to the rubber.

As specific examples of the copolymer (B) having a functional group reactive with the liquid crystal polyester, rubbers having an epoxy group include (meth) acrylate-ethylene- (unsaturated glycidyl carboxylate and And / or unsaturated glycidyl ether) copolymer rubber.

Here, the (meth) acrylate is
An ester obtained from acrylic acid or methacrylic acid and an alcohol. Alcohols have 1 carbon atom
~ 8 alcohols are preferred. Specific examples of (meth) acrylates include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, ter
Examples thereof include t-butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. As the (meth) acrylic acid ester, one kind thereof may be used alone, or two or more kinds may be used in combination.

In the copolymer rubber of the present invention, the content of (meth) acrylate unit is preferably more than 40% by weight and less than 97% by weight, more preferably 45 to 70% by weight.
% By weight, the ethylene unit is 3% by weight or more and less than 50% by weight,
More preferably, the content is 10 to 49% by weight, and the content of unsaturated carboxylic acid glycidyl ether units and / or unsaturated glycidyl ether units is 0.1 to 30% by weight, more preferably 0.5 to 20% by weight. If it is outside the above range,
The thermal stability and mechanical properties of the resulting molded product such as a film or sheet may be insufficient, which is not preferable.

The copolymer rubber can be produced by a conventional method, for example, bulk polymerization, emulsion polymerization, solution polymerization or the like using a free radical initiator. Typical polymerization methods are described in JP-B-46-45085 and JP-B-6-45085.
1-1127709, etc.,
Pressure of 5 in the presence of a free radical generating polymerization initiator
It can be manufactured under the conditions of at least 00 kg / cm ² and a temperature of 40 to 300 ° C.

Other examples of the rubber that can be used for the copolymer (B) include an acrylic rubber having a functional group reactive with the liquid crystal polyester and a vinyl aromatic having a functional group reactive with the liquid crystal polyester. A hydrocarbon compound-conjugated diene compound block copolymer rubber can also be exemplified.

The acrylic rubber mentioned here is preferably represented by the general formula (1) (In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms or a cyanoalkyl group.), A general formula (2) (Wherein, R ² is an alkylene group having 1 to 12 carbon atoms, R ³
Represents an alkyl group having 1 to 12 carbon atoms. ) And general formula (3) (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ^{5 is} an alkylene group having 3 to 30 carbon atoms, R ⁶ is an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and n is an integer of 1 to 20) ) As a main component.

Specific examples of the alkyl acrylate represented by the general formula (1) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Examples thereof include butyl acrylate, pentyl acrylate, hexyl acrylate, actyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, and cyanoethyl acrylate.

Examples of the alkoxyalkyl acrylate represented by the general formula (2) include methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, and ethoxypropyl acrylate. One or more of these can be used as the main component of the acrylic rubber.

As a constituent component of the acrylic rubber, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the above general formulas (1) to (3), if necessary. Can be used. Examples of such unsaturated monomers include styrene, α-methylstyrene, acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinylnaphthalene, N-methylolacrylamide, vinyl acetate, vinyl chloride, chloride Vinylidene, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

The preferred constituent ratio of the acrylic rubber having a functional group reactive with the liquid crystal polyester is at least one monomer selected from the compounds represented by the above general formulas (1) to (3). 0 to 99.9% by weight, 0.1 to 30.0% by weight of unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether, selected from the compounds represented by the above general formulas (1) to (3). Unsaturated monomer copolymerizable with at least one monomer 0.0
３30.0% by weight. When the constituent ratio of the acrylic rubber is within the above range, heat resistance and impact resistance of the composition,
The molding processability is good and preferable.

The method for producing the acrylic rubber is not particularly limited. For example, JP-A-59-113010, JP-A-62-64809, and JP-A-3-160008
Or a well-known polymerization method described in, for example, WO 95/04764, and can be produced by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization in the presence of a radical initiator. be able to.

As the vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with the liquid crystal polyester, preferably,
Rubber obtained by epoxidizing a block copolymer consisting of (a) a sequence mainly composed of a vinyl aromatic hydrocarbon compound and (b) a sequence mainly composed of a conjugated diene compound, or a hydrogenated product of the block copolymer Is a rubber obtained by epoxidation of

The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or its hydrogenated product can be produced by a well-known method.
798 and JP-A-59-133203.

As the aromatic hydrocarbon compound, for example,
Styrene, vinyltoluene, divinylbenzene, α-methylstyrene, p-methylstyrene, vinylnaphthalene and the like can be mentioned, among which styrene is preferable.
Examples of the conjugated diene compound include butadiene, isoprene, pyrrylene, 1,3-pentadiene, 3-butyl-1,3-octadiene and the like, butadiene or isoprene is preferred.

The rubber used as the copolymer (B) is preferably (meth) acrylate-ethylene-
(Unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is used.

The rubber used as the copolymer (B) can be vulcanized as required and used as a vulcanized rubber. The above (meth) acrylic acid ester-ethylene-
Vulcanization of the (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is achieved by using a polyfunctional organic acid, a polyfunctional amine compound, an imidazole compound, and the like. It is not limited.

Further, as a specific example of the copolymer (B) having a functional group reactive with the liquid crystal polyester, a thermoplastic resin having an epoxy group includes (a) 50 to 99% by weight of ethylene units, b) 0.1 to 30% by weight, preferably 0.5 to 2% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units.
0% by weight and (c) an epoxy group-containing ethylene copolymer in which the ethylenically unsaturated ester compound unit is 0 to 50% by weight.

Examples of the ethylenically unsaturated ester compound (c) include vinyl carboxylate such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. Esters, α, β-unsaturated carboxylic acid alkyl esters, and the like. Particularly, vinyl acetate, methyl acrylate and ethyl acrylate are preferred.

Specific examples of the epoxy group-containing ethylene copolymer include, for example, a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units and glycidyl methacrylate units, and a methyl acrylate unit. Copolymers composed of glycidyl methacrylate units and ethyl acrylate units, and copolymers composed of ethylene units, glycidyl methacrylate units and vinyl acetate units are exemplified.

The melt index of the epoxy group-containing ethylene copolymer (hereinafter, may be referred to as MFR. JI.
SK6760, 190 ° C., 2.16 kg load) is preferably 0.5 to 100 F-10 minutes, more preferably 2 to 100 F-10 minutes.
~ 50F-10 minutes. The melt index may be outside this range, but the melt index is 100F
If it exceeds -10 minutes, it is not preferable from the viewpoint of mechanical properties of the composition, and if it is less than 0.5F-10 minutes, the compatibility with the liquid crystal polyester of the component (A) is inferior.

[0054] Also, the epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2. If the flexural rigidity is outside this range, the molding processability and mechanical properties of the composition may be insufficient, which is not preferable.

The ethylene copolymer containing an epoxy group is usually prepared by reacting an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence of a suitable solvent or a chain transfer agent. It is produced by a high-pressure radical polymerization method in which copolymerization is carried out in the presence. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt-grafted and copolymerized in an extruder.

The liquid crystal polyester resin composition mentioned as a preferred specific example of the liquid crystal polymer used in the present invention is a copolymer having (A) a liquid crystal polyester as a continuous phase and (B) a functional group reactive with the liquid crystal polyester. Is a resin composition having a dispersed phase. When the liquid crystal polyester is not in a continuous phase, the gas barrier properties, heat resistance, and the like of a molded product such as a film or sheet using the liquid crystal polyester resin composition may be significantly reduced.

Although the details of the mechanism of the resin composition of the copolymer having a functional group and the liquid crystal polyester are not clear, the components (A) and (B) of the composition may have a different composition. It is considered that a reaction occurs, and the component (A) forms a continuous phase, and the component (B) is finely dispersed, thereby improving the moldability of the composition.

One embodiment of the liquid crystal polyester resin composition comprises (A) 56.0 to 99.9% by weight of liquid crystal polyester, preferably 65.0 to 99.9% by weight, and more preferably 70 to 98% by weight. And (B) a copolymer having a functional group reactive with the liquid crystal polyester 44.0 to 44.0.
The resin composition contains 0.1% by weight, preferably 35.0 to 0.1% by weight, and more preferably 30 to 2% by weight. If the content of the component (A) is less than 56.0% by weight, the gas barrier properties and heat resistance of a molded article such as a film or sheet obtained from the composition may be undesirably reduced.
On the other hand, if the content of the component (A) exceeds 99.9% by weight, the molding processability of the composition may be reduced, and the composition is expensive, which is not preferable.

As a method for producing the liquid crystal polyester resin composition, a known method can be used. For example, mixing each component in a solution state and evaporating the solvent,
A method of precipitating in a solvent may be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferred. For the melt kneading, kneading apparatuses such as a single-screw or twin-screw extruder and various kneaders which are generally used can be used. In particular, a biaxial high kneader is preferred. During melt kneading, the cylinder set temperature of the kneading device is 200 to 360 ° C.
Is more preferable, and more preferably 230 to 350 ° C.
It is.

At the time of kneading, the respective components may be previously mixed uniformly using a device such as a tumbler or a Henschel mixer. If necessary, the mixing may be omitted, and the components may be separately supplied to the kneading device. Methods can also be used.

The liquid crystalline polymer used in the present invention may contain, if necessary, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an inorganic or organic colorant, a rust inhibitor,
Various additives such as a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a mold release improving agent such as a fluororesin can be added during the manufacturing process or in the subsequent processing process.

As the layer composed of the liquid crystalline polymer used in the present invention, the liquid crystalline polymer is formed by, for example, a T-die method in which the molten resin is extruded and wound from a T-die, or the molten resin is formed into a cylindrical shape by an extruder provided with an annular die. The film or sheet obtained by the inflation film forming method, the film or sheet obtained by the hot press method or the solvent casting method, or the sheet obtained by the injection molding method or the extrusion method is further uniaxially stretched. Alternatively, a film or sheet obtained by biaxial stretching can be used. In the case of injection molding, extrusion molding, or the like, a film or sheet can be obtained by dry blending the component pellets at the time of molding and melt-molding them without going through a kneading step in advance.

In the T-die method, a uniaxially stretched film or a biaxially stretched film obtained by winding a molten resin extruded through a T-die while stretching it in the winder direction (longitudinal direction) is preferably used.

The conditions for setting the extruder at the time of forming the uniaxially stretched film can be appropriately set according to the composition of the composition, but the cylinder temperature is preferably in the range of 200 to 360 ° C., and more preferably in the range of 230 to 350 ° C. More preferred. If the ratio is outside this range, thermal decomposition of the composition may occur or film formation may be difficult, which is not preferable.

The slit interval of the T-die is 0.2 to 2.0.
mm is preferable, and 0.2 to 1.2 mm is more preferable.
The draft ratio of the uniaxially stretched film is preferably in the range of 1.1 to 40, more preferably 10 to 40, and particularly preferably 15 to 35.

The draft ratio referred to here is a value obtained by dividing the cross-sectional area of the T-die slit by the cross-sectional area of the film perpendicular to the longitudinal direction. If the draft ratio is less than 1.1, the film strength is insufficient, and if the draft ratio exceeds 45, the surface smoothness of the film may be insufficient, which is not preferable. The draft ratio can be set by controlling the setting conditions of the extruder, the winding speed, and the like.

For the biaxially stretched film, the same extruder setting conditions as those for forming the uniaxially stretched film, ie, the cylinder temperature is preferably in the range of 200 to 370 ° C., more preferably in the range of 230 to 360 ° C. The composition is melt-extruded at a slit interval of preferably 0.2 to 1.2 mm, and the melt sheet extruded from the T-die is simultaneously stretched in the longitudinal direction and the direction perpendicular to the longitudinal direction (lateral direction). The melt sheet extruded from the T-die is first stretched in the longitudinal direction, and then the stretched sheet is stretched in the same process in a transverse direction from a tenter in a high temperature atmosphere of 100 to 340 ° C. by a successive stretching method. can get.

When a biaxially stretched film is obtained, the stretching ratio is preferably 1.2 to 20 times in the longitudinal direction and 1.2 to 20 times in the transverse direction. If the stretching ratio is outside the above range, the strength of the composition film may be insufficient, and it may be difficult to obtain a film having a uniform thickness.

Further, an inflation film obtained by forming a melt sheet extruded from a cylindrical die by inflation is also preferably used.

That is, the liquid crystal polyester resin composition obtained by the above method is supplied to a melt-kneading extruder equipped with a die having an annular slit, and the cylinder is set at a temperature of preferably 200 to 370 ° C., more preferably 230 to 3 ° C.
It is melt-kneaded at 60 ° C. Next, the molten resin is extruded upward or downward from the annular slit of the extruder to form a cylindrical film (this direction is the MD direction). The annular slit interval is usually 0.1 to 5 mm, preferably 0.2 to 2 m
m, the diameter of the annular slit is usually 20 to 1000 mm, preferably 25 to 600 mm.

Draft is applied to the melt-extruded molten resin film in the longitudinal direction (MD), and air or an inert gas, for example, nitrogen gas is blown from the inside of the cylindrical film so that a transverse direction perpendicular to the longitudinal direction is obtained. The film is expanded and stretched in (TD).

In inflation molding (film formation),
The preferred blow ratio is 1.5 to 10, and the preferred MD draw ratio is 1.5 to 40. If the setting conditions during the inflation film formation are outside the above range, it may be difficult to obtain a high-strength liquid crystal polyester resin composition film having a uniform thickness and no wrinkles.

The expanded film is usually air-cooled or water-cooled on its circumference and then passed through a nip roll and taken off.

In the case of inflation film formation, conditions can be selected according to the composition of the liquid crystal polyester resin composition such that the cylindrical melt film expands to a uniform thickness and a smooth surface.

The thickness of the layer comprising the liquid crystalline polymer in the present invention is not particularly limited, but is preferably 3 to 1000.
μm, and more preferably 5 to 200 μm. In the present invention, a film composed of a liquid crystalline polymer and a laminated film composed of a thermoplastic resin (excluding the liquid crystalline polymer) and / or paper can be used for wallpaper.
Thermoplastic resin (excluding liquid crystalline polymer)
Is not particularly limited, but polyolefin is preferable.

As the layer made of the thermoplastic resin (excluding the liquid crystal polymer), a film obtained by the same method as in the above-mentioned method for producing a film made of a liquid crystal polymer or by appropriately changing the same is used. Can be. The thickness of the layer made of the thermoplastic resin (excluding the liquid crystalline polymer) is not particularly limited, but is 5 to 2000 μm.
The range of m is preferred. The surface of the film made of the thermoplastic resin can be treated in advance with an anchor coat agent.

In the present invention, the surface of a film made of a liquid crystalline polymer and / or the surface of a thermoplastic resin (excluding the liquid crystalline polymer) can be subjected to a surface treatment in advance. Examples of such a surface treatment method include corona discharge treatment, plasma treatment, flame treatment, sputtering treatment, solvent treatment, ultraviolet treatment, polishing treatment, infrared treatment, and ozone treatment.

Paper can be used as a component of the wallpaper in the present invention. The paper is not particularly limited, and a well-known paper can be used.
Paper and a film made of a liquid crystalline polymer or a film made of a thermoplastic resin (excluding a thermoplastic resin) can be bonded to each other with an adhesive interposed therebetween.

The lamination of a film composed of a liquid crystalline polymer and a film composed of a thermoplastic resin (excluding the liquid crystalline polymer) and / or paper is performed in the order of a film composed of a liquid crystalline polymer / a film composed of a thermoplastic resin / paper. Or in the order of paper / film composed of thermoplastic resin / film composed of liquid crystalline polymer / film composed of thermoplastic resin. When it is necessary to treat stains on the wallpaper surface with a chemical, it is preferable that a film made of a liquid crystalline polymer having excellent chemical resistance is provided on the outermost side. In the present invention, a film formed of a liquid crystal polymer and a film formed of a thermoplastic resin (excluding a liquid crystal polymer) or a film formed of a thermoplastic resin are bonded by thermocompression bonding, ultrasonic fusion, or an adhesive. Can be glued.

In the wallpaper of the present invention, since a film made of a liquid crystalline polymer has a high barrier property against volatile organic compounds, the scattering of volatile organic compounds, for example, formaldehyde from inside the building material into the room through the wallpaper is greatly reduced. It is effective in preventing sick house syndrome. Further, the wallpaper of the present invention, even when the film made of the liquid crystalline polymer is contaminated with ink, paint or food, drink, etc., because the film made of the liquid crystalline polymer has excellent chemical resistance, It is highly possible to remove the contamination by treating the contaminated portion of the film with a suitable chemical without damaging the film made of the conductive polymer itself.

[0081]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. (1) Liquid crystal polyester of component (A) (i) 8.3 kg (60 mol) of p-acetoxybenzoic acid, 2.49 kg (15 mol) of terephthalic acid, 0.83 kg (5 mol) of isophthalic acid and 4,4 ′ 5.45 kg (20.2 mol) of diacetoxydiphenyl was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was increased while stirring under a nitrogen gas atmosphere to carry out polymerization at 330 ° C. for 1 hour. During this time, polymerization was carried out under strong stirring while liquefying and collecting and removing acetic acid gas produced as a by-product in a cooling tube. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system.
The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This is further heated at 280 ° C. in a rotary kiln under a nitrogen gas atmosphere.
For 3 hours to obtain a particulate wholly aromatic polyester having a flow temperature of 324 ° C. and comprising the following repeating structural units. Here, the flow temperature refers to a resin heated at a heating rate of 4 ° C./min using a Shimadzu Koka type flow tester model CFT-500 and a load of 100 kgf / c.
When extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under m ² , this refers to a temperature at which the melt viscosity shows 48,000 poise. Hereinafter, the liquid crystal polyester is abbreviated as A-1. This polymer showed optical anisotropy at 340 ° C. or more under pressure. The repeating structural units of the liquid crystal polyester A-1 are as follows.

[0082]

(2) Component (B) (i) According to the method described in Example 5 of JP-A-61-227709, methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38.7 / 2.3
(Weight ratio), Mooney viscosity = 15, heat of fusion of crystal <1
A rubber of J / g was obtained. Hereinafter, the rubber may be abbreviated as B-1. Here, the Mooney viscosity is JIS K6300
It is a value measured using a large rotor at 100 ° C. according to The heat of fusion of the crystal was determined by using a DSC and heating the sample from -150 ° C to 100 ° C at a rate of 20 ° C / min.

(3) Method for measuring physical properties The obtained films and wallpapers were measured in the following manner. (I) Oxygen gas permeability: Oxygen permeability measuring device (OX-TRAN 10/5) according to JIS K7126 isobaric method
0A, manufactured by MOCON) and the test gas was oxygen 99
%, Carrier gas is 98% nitrogen, 2% hydrogen, temperature 23
C., the relative humidity on the test gas side was 60%, and the relative humidity on the carrier gas side was 60%. Unit is cc / m ² · 24hr
・ It is 1 atm. Water vapor transmission rate: JIS Z0208
According to the (cup method), the measurement was performed under the conditions of a temperature of 40 ° C. and a relative humidity of 60%. The unit is g / m ²・ 24hr ・ 1atm
It is.

Example 1 A-1 was mixed at 80% by weight and B-1 at 20% by weight.
Using a TEX-30 twin screw extruder manufactured by Nippon Steel Corporation, cylinder set temperature 350 ° C, screw rotation speed 200r
The composition was obtained by melt-kneading at pm. The flow start temperature of the composition was 328 ° C. Also, the composition is 340
It showed optical anisotropy above ℃. A pellet of this composition is supplied to a 60 mmφ single screw extruder equipped with a cylindrical die, melt-kneaded at a cylinder set temperature of 350 ° C. and a rotation speed of 60 rpm, and has a diameter of 50 mm, a lip interval of 1.0 mm, and a die set temperature of 355 ° C. The molten resin is extruded upward from the cylindrical die, and at this time, dry air is press-fitted into the hollow portion of the cylindrical film to expand the cylindrical film, and then cooled and then passed through a nip roll at a take-up speed of 75 m / min. Taking over,
A film composed of a liquid crystalline polymer to be used for wallpaper was obtained. At this time, the stretching ratio in the film MD direction is 20.5,
The blow ratio was 4.1 and the film thickness was 12 μm.
The oxygen permeability of the film is 7 cc / m ² · 24 hr ·
1 atm, water vapor permeability: 0.6 g / m ² · 24 hr
・ It was 1 atm.

A mark was formed on the surface of the film made of the liquid crystalline polymer with Magic Ink (manufactured by Mitsubishi Pencil Co., Ltd.) (red, rough), and after 24 hours, the film was marked with a cloth impregnated with acetone. After rubbing the place
The mark disappeared completely, and no scratch was left on the film. After 2 cc of the reagent formaldehyde was placed in an aluminum container having a capacity of about 15 cc, the container was sealed with a film made of the liquid crystalline polymer, and the odor was removed. As a result, no odor of formaldehyde was felt. Two weeks after the sealing, the odor was similarly smelled, but no odor of formaldehyde was felt.

[0087]

The wallpaper of the present invention has good gas barrier properties and chemical resistance, high barrier properties against volatile organic compounds such as formaldehyde, and is an inexpensive wallpaper. is there.

Continued on front page F-term (reference) 2H088 EA65 GA06 MA20 4F100 AK01A AK01B AK03B AK04A AK04J AK24A AK24J AK25A AK25J AK41A AL01A AL05A AN00A BA02 BA41A DG10B GB08 JA06A JA11AJB18 J02B30

Claims (17)

[Claims] 1. A wallpaper using a film made of a liquid crystalline polymer that exhibits optical anisotropy when melted. 2. A film comprising a liquid crystalline polymer exhibiting optical anisotropy when melted and a laminated film composed of a thermoplastic resin (excluding the liquid crystalline polymer) and / or paper. And wallpaper. 3. The wallpaper according to claim 2, wherein the thermoplastic resin is a polyolefin. 4. A liquid crystalline polymer which exhibits optical anisotropy when melted comprises (A) a liquid crystalline polyester as a continuous phase, and (B) a copolymer having a functional group reactive with the liquid crystalline polyester as a dispersed phase. The wallpaper according to any one of claims 1 to 3, which is a liquid crystal polyester resin composition. 5. A liquid crystalline polymer exhibiting optical anisotropy when melted comprises (A) 56.0 to 99.9% by weight of a liquid crystalline polyester and (B) a copolymer having a functional group reactive with the liquid crystalline polyester. 2. A composition obtained by melt-kneading 44.0 to 0.1% by weight of a polymer.
The wallpaper according to any one of to 4. 6. The wallpaper according to claim 5, wherein the functional group reactive with the liquid crystal polyester is an oxazolyl group, an epoxy group or an amino group. 7. The copolymer (B) having a functional group reactive with the liquid crystal polyester, wherein the copolymer (B) contains 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. The wallpaper according to any one of claims 5 to 6, which is a polymer. 8. The copolymer (B) having a functional group reactive with a liquid crystal polyester has a crystal heat of fusion of 3 J / g.
The wallpaper according to any one of claims 5 to 7, which is a copolymer having a weight of less than or equal to. 9. The method according to claim 5, wherein the Mooney viscosity of the copolymer (B) having a functional group reactive with the liquid crystal polyester is in the range of 3 to 70. wallpaper. The Mooney viscosity referred to here is JIS K6
It refers to a value measured using a large rotor at 100 ° C. according to 300. 10. The wallpaper according to claim 5, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a rubber having an epoxy group. 11. The rubber having an epoxy group comprises a (meth) acrylate-ethylene- (unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether) copolymer rubber.
The described wallpaper. 12. The method according to claim 12, wherein the (meth) acrylate is methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate,
The wallpaper according to claim 11, comprising at least one selected from the group consisting of -ethylhexyl acrylate and 2-ethylhexyl methacrylate. 13. The wallpaper according to claim 4, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a thermoplastic resin having an epoxy group. 14. A thermoplastic resin having an epoxy group,
(A) 50 to 99% by weight of ethylene units, (b) 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units,
(C) 0-50 ethylenically unsaturated ester compound units
14. The wallpaper according to claim 13, which is an epoxy group-containing ethylene copolymer in an amount of 0.1% by weight. 15. The wallpaper according to claim 4, wherein the liquid crystal polyester (A) contains at least 30 mol% of the following repeating structural units. 16. A liquid crystal polyester (A) obtained by reacting an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid with each other. The described wallpaper. 17. The wallpaper according to any one of claims 4 to 14, wherein the liquid crystal polyester (A) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids.