JP5047008B2 - Antifouling film for wallpaper and wall covering - Google Patents

Description

The present invention can be produced by a method such as coextrusion without using an organic solvent, and has a strong adhesive force even when the vinyl chloride layer contains a high-boiling plasticizer. It is related with the antifouling film for wallpaper and wall covering material which are excellent in antifouling property and antiblocking property.

As wallpaper used by being attached to indoor walls, closets, furniture, and the like, vinyl chloride wallpaper including a vinyl chloride layer is frequently used because of its excellent physical properties, good moldability and low cost. However, there is a problem that the vinyl chloride wallpaper is easily soiled, and that once it is soiled, it is difficult to remove the soil. In addition, since the vinyl chloride wallpaper generally contains a plasticizer, the plasticizer bleeds on the surface, and there is a problem that dirt easily occurs due to adhesion of suspended matters in the air.

Therefore, as one of the means for imparting antifouling properties to vinyl chloride wallpaper, an antifouling film having an adhesive layer formed on a base material layer made of a resin having antifouling properties is applied to the surface of the vinyl chloride layer of the vinyl chloride wallpaper. A method of laminating and bonding to each other is known. Conventionally, as such a base material layer, ethylene-vinyl acetate copolymer saponified product (EVOH) or an acrylic film has been used, and in particular, an EVOH film has been widely used.
For example, Patent Document 1 discloses an antifouling film using a transparent biaxially stretched polyester film as a base material layer. For example, Patent Document 2 uses a copolymerized polyester film as a base material layer. An antifouling film was disclosed.

Properties required for such an antifouling film include strong adhesion to the surface of the vinyl chloride layer in addition to the antifouling property of the base material layer. In particular, when the surface of the vinyl chloride wallpaper is embossed to form fine irregularities and give three-dimensional design, the antifouling film is lifted from the surface of the vinyl chloride layer, and the appearance of the vinyl chloride wallpaper is improved. Therefore, strong adhesion to the surface of the vinyl chloride layer has been required.

However, the conventional antifouling film has insufficient adhesion to the surface of the vinyl chloride layer at a low temperature, so that the antifouling film is firmly bonded to the surface of the vinyl chloride layer at a high temperature of 100 ° C. or higher. Had to be processed. However, when the vinyl chloride layer containing a plasticizer is heated to 100 ° C. or higher, there is a problem that the plasticizer bleeds out on the surface of the vinyl chloride layer.

Further, in the conventional antifouling film, an adhesive layer is formed by a so-called coating method or the like in which a solution obtained by dissolving a resin in an organic solvent is applied on a substrate and then dried. However, in recent years, as a countermeasure against volatile organic compounds (VOC) such as toluene and xylene, it has been required to form an adhesive layer without using an organic solvent. A method of directly forming an adhesive layer on a substrate by coextrusion molding has been studied.
If the adhesive layer can be formed by coextrusion molding, it is not necessary to perform the coating process and the drying process, which not only simplifies the process, but the formed adhesive layer is a substrate unlike the coating method. There are few variations in the repellency and thickness of the adhesive layer due to the difference in surface condition.

Therefore, the present inventors disclosed in Patent Document 3 an antifouling film for wallpaper having an antifouling layer made of crystalline polypropylene and an adhesive layer made of amorphous polyester having a predetermined glass transition temperature. Among them, a method for forming an adhesive layer by coextrusion is disclosed. Such a wallpaper antifouling film has antifouling properties and strong adhesion to the surface of the vinyl chloride layer, and has high antiblocking properties and excellent handleability.

However, in recent years, as a measure against VOC, a plasticizer with a high boiling point is used in the vinyl chloride layer, and the plasticizer tends to remain in the wallpaper. Therefore, when using such an antifouling film for wallpaper, Even in such a case, the adhesive strength may be lowered after a long period of time.
So, even if the vinyl chloride layer contains a high-boiling plasticizer while having antifouling properties, anti-blocking properties, and adhesion to the base material layer required as an antifouling film for wallpaper, There has been a demand for an antifouling film for wallpaper in which the adhesive strength does not decrease over a long period of time.
Japanese Patent Application Laid-Open No. 07-232415 JP 07-290667 A JP 2004-332367 A

In view of the above situation, the present invention can be produced by a method such as coextrusion molding without using an organic solvent, and the vinyl chloride layer contains a high-boiling plasticizer. An object of the present invention is to provide an antifouling film for wall paper and a wall covering material that maintains a strong adhesive force and is excellent in antifouling properties and antiblocking properties.

The antifouling film for wallpaper of the present invention is an antifouling film for wallpaper used for vinyl chloride wallpaper containing a high-boiling plasticizer, comprising a polypropylene resin layer comprising a crystalline polypropylene resin and a sulfone group A polyester resin layer made of a polyester resin is laminated via an adhesive layer, and the adhesive layer contains a modified styrene elastomer and / or a modified polyolefin resin, and constitutes the polyester resin layer The antifouling film for wallpaper contains 1.2 to 30 mol% of sulfone groups with respect to the whole.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention can use a sulfone group-containing polyester resin containing a predetermined amount of a sulfone group as the polyester resin constituting the polyester resin layer, and can be molded by coextrusion molding. Antifouling film for wallpaper that has excellent antifouling properties and antiblocking properties, and can maintain high adhesive strength over a long period of time even when used for vinyl chloride wallpaper containing high-boiling plasticizers As a result, the present invention has been completed.

The antifouling film for wallpaper of the present invention has a polyester resin layer made of a sulfone group-containing polyester resin. By containing the sulfone group-containing polyester resin, the polyester resin layer can maintain strong adhesive strength between the polypropylene resin layer and the polyester resin layer even in the presence of a plasticizer.
As said sulfone group containing polyester-type resin, single resin may be used and 2 or more types of resin may be mixed and used. Further, a sulfone group-containing polyester resin and a polyester resin not containing a sulfone group may be mixed and used.

As said sulfone group containing polyester-type resin, the polyester resin etc. which are obtained by mix | blending a sulfone group containing dicarboxylic acid and / or a sulfone group containing diol with dicarboxylic acid and / or diol are mentioned, for example.
The sulfone group includes not only the acid form but also a salt form. Examples of the salt form include alkali metal salts and tertiary amine salts.

The dicarboxylic acid is not particularly limited. For example, o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octyl succinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid , Maleic acid, itaconic acid, decamethylene carboxylic acid, their anhydrides and lower alkyl esters.
The diol is not particularly limited. For example, ethylene glycol, 1,3-propanediol, 1,4 butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, triethylene glycol , Tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol, (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol Aliphatic diols such as 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; Alkylene oxide addition of hydroxycyclohexyl) propane , 1,4-cyclohexanediol, alicyclic diols such as 1,4-cyclohexanedimethanol.

Examples of the sulfone group-containing dicarboxylic acid include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 3-sulfophthalic acid, dialkyl 5-sulfoisophthalate, dialkyl 2-sulfoisophthalate, 4- Examples include dialkyl sulfoisophthalate, dialkyl 3-sulfoisophthalate, and sodium salts and potassium salts thereof.
Examples of the sulfone group-containing diol include 1,3-dihydroxybutanesulfonic acid, 1,4-dihydroxybutanesulfonic acid, and the like.

The minimum of content of the said sulfone group is 1.2 mol% with respect to the whole resin which comprises the said polyester-type resin layer. When it is less than 1.2 mol%, the adhesive strength between the polypropylene resin layer and the polyester resin layer becomes insufficient in the presence of a plasticizer. A preferable upper limit is 30 mol%. If it exceeds 30 mol%, sufficient adhesive strength between the polyester resin layer and the vinyl chloride layer of the vinyl chloride wallpaper may not be obtained. A more preferred upper limit is 20 mol%.
In addition, the said sulfone group content can be measured by performing a < ¹ > H-NMR measurement about the polyester-type resin layer of the antifouling film for wallpaper of this invention, for example.

The minimum with a preferable glass transition point of the said sulfone group containing polyester-type resin is 35 degreeC, and a preferable upper limit is 100 degreeC. By setting it within the above range, it is possible to obtain an antifouling film for wallpaper that is not only firmly bonded to the vinyl chloride wallpaper by thermocompression bonding but also excellent in embossing ability. That is, the sulfone group-containing polyester resin is very excellent in the embossability, so even if the polypropylene resin layer lacks the embossability, the antifouling film for wallpaper of the present invention has an embossability. Excellent film. Therefore, even a crystalline polypropylene resin that has not been a good product due to lack of embossing properties can be effectively used as a material for the polypropylene resin layer in the present invention.
When the glass transition point is less than 35 ° C., the resulting antifouling film for wallpaper has poor thermal stability, and the films may block each other. When it exceeds 100 ° C., the thermocompression bonding property with the polyvinyl chloride wallpaper may be deteriorated. A more preferred lower limit is 50 ° C., a more preferred upper limit is 95 ° C., and a still more preferred upper limit is 90 ° C.

The preferable lower limit of the intrinsic viscosity of the sulfone group-containing polyester resin is 0.4 dl / g, and the more preferable lower limit is 0.5 dl / g. If it is less than 0.4 dl / g, the film strength becomes weak, and the adhesive strength with the vinyl chloride wallpaper may also become weak.

The polyester resin layer may be unstretched or stretched, but it is desirable that the polyester resin layer be unstretched from the viewpoint of thermal stability. Moreover, you may perform well-known surface treatments, such as a corona discharge process, on the surface of the said polyester-type resin layer.

Depending on the purpose, the polyester resin layer may be blended with a resin other than the sulfone group-containing polyester resin. Examples of the resin to be blended include binary copolymers and ternary copolymers composed of polyethylene, ethylene and monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester.

In addition to the resins described above, additives such as antistatic agents, antiblocking agents, lubricants, fillers, colorants and the like may be added to the polyester resin layer as long as the effects of the present invention are not impaired. Good.

Although it does not specifically limit as thickness of the said polyester-type resin layer, A preferable minimum is 1 micrometer and a preferable upper limit is 20 micrometers. When the thickness is less than 1 μm, the adhesive force between the antifouling film for wallpaper of the present invention and the vinyl chloride wallpaper may be insufficient, and the adhesive force tends to vary. If it exceeds 20 μm, the manufacturing cost will increase, and the polypropylene resin layer made of crystalline polypropylene resin will be warped, or the design such as the pattern shown on the surface of the vinyl chloride wallpaper may be concealed. The flexibility of the antifouling film for wallpaper may be reduced.

The polyester resin layer is preferably 0.05 times or more, more preferably 0.1 times or more the thickness of the polypropylene resin layer. If it is less than 0.05 times, the embossing followability to the polypropylene resin layer may be insufficient.

In the antifouling film for wallpaper of the present invention, the resin constituting the adhesive layer is not particularly limited, and a commercially available adhesive resin can be used, but a resin having a polar group may be used. preferable.
Examples of the polar group include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, and a sulfonic acid chloride. Group, sulfonic acid amide group, sulfonic acid group, epoxy group, amino group, imide group, oxazoline group, hydroxyl group and the like.
In addition, as a method of introducing the polar group, for example, a method of grafting maleic anhydride or the like, a compound having a functional group such as an amine compound or a carboxylic acid compound is reacted, and an amine or a carboxylic acid is added to the terminal portion. And the like.

As the resin having a polar group, it is preferable to use a resin composed of a modified styrene elastomer and / or a modified polyolefin resin.
The adhesive layer made of the modified styrene elastomer and / or the modified polyolefin resin has high affinity with both the polypropylene resin and the polyester resin, and can bond both with high strength. Moreover, since it can shape | mold by the co-extrusion method with the said polypropylene-type resin layer and the polyester-type resin layer, it is excellent also in productivity.

Examples of the modified styrene elastomer include a styrene elastomer composed of polystyrene as a hard segment and polybutadiene, polyisoprene, a copolymer of polybutadiene and polyisoprene as a soft segment, and a hydrogenated product of the styrene elastomer. The thing modified | denatured with the polar group is mentioned. As the polar group used in this case, for example, a carboxylic acid group, an acid anhydride group, an amino group, an epoxy group, a hydroxyl group and the like are preferable. The hydrogenated product may be one obtained by hydrogenating a part of prebutadiene or polyisoprene, or may be one obtained by hydrogenating all of them.
Specifically, for example, maleic anhydride modified styrene-ethylene / butylene-styrene block copolymer (maleic anhydride modified SEBS resin), maleic anhydride modified styrene-ethylene / propylene-styrene block copolymer (maleic anhydride modified) SEPS resin), epoxy resin-modified styrene-ethylene / butylene-styrene block copolymer (epoxy-modified SEBS resin), epoxy resin-modified styrene-ethylene / propylene-styrene block copolymer (epoxy-modified SEPS resin), and the like.

The minimum with preferable content of the said polar group in the said modified styrene-type elastomer is 0.05 weight%, and a preferable upper limit is 5.0 weight%. If it is less than 0.05% by weight, adhesion to the polyester resin layer may be insufficient, and if it exceeds 5.0% by weight, the resin is thermally deteriorated when the functional group is added, Foreign matter such as gel may be easily generated. A more preferred lower limit is 0.1% by weight, and a more preferred upper limit is 3.0% by weight.

Examples of commercially available modified styrene elastomers include, for example, trade names “Tuftec”, “Tufprene” (all manufactured by Asahi Kasei Chemicals), “Clayton” (manufactured by Kraton Polymer), “Dynalon” (manufactured by JSR), “Septon” (manufactured by Kuraray Co., Ltd.)

The modified polyolefin resin refers to a resin mainly composed of a polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof, a silane coupling agent or the like (hereinafter also simply referred to as a modified monomer).
Examples of the unsaturated carboxylic acid or anhydride thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride and the like. In addition, a monoepoxy compound of the unsaturated carboxylic acid or its derivative and an ester compound of the unsaturated carboxylic acid or its anhydride, a functional group capable of reacting with the unsaturated carboxylic acid or its anhydride in the molecule You may use the reaction product of the polymer which has this, the said unsaturated carboxylic acid, or its anhydride. Furthermore, the metal salt of the said unsaturated carboxylic acid can also be used. Of these, maleic anhydride is more preferably used. Moreover, the said unsaturated carboxylic acid or its anhydride may be used independently, and may use 2 or more types together.

Examples of the silane coupling agent include vinyltriethoxysilane, methacryloyloxytrimethoxysilane, and γ-methacryloyloxypropyltriacetyloxysilane.

As a method for producing the modified polyolefin resin, for example, a method of copolymerization by adding and mixing a modified monomer in advance during polymerization may be used. After the polyolefin resin is polymerized, the modified monomer is graft copolymerized. You may use the method to make. Of these, a method by graft copolymerization is preferred.
Moreover, when manufacturing the said modified polyolefin resin, the minimum with preferable content of the said modified monomer is 0.1 mass%, and a preferable upper limit is 5 mass%.

Examples of commercially available modified polyolefin resins include “Admer” (manufactured by Mitsui Chemicals), “Modic” (manufactured by Mitsubishi Chemical Corporation), and the like.

In the antifouling film for wallpaper of the present invention, the thickness of the adhesive layer is not particularly limited and is appropriately determined in consideration of the performance, price, etc. of the antifouling film for wallpaper of the present invention. 1 μm and a preferable upper limit is 20 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength between the polypropylene resin layer and the polyester resin layer may not be obtained. When the thickness exceeds 20 μm, the manufacturing cost increases, and the design such as a design represented on the surface of the vinyl chloride layer may be concealed or the handleability may be deteriorated.

In the adhesive layer constituting the antifouling film for wallpaper of the present invention, in addition to the above-mentioned materials, an antistatic agent, an anti-blocking agent, a lubricant, and a filler are added as long as the properties as the adhesive layer are not impaired. Additives such as colorants may be added, or other resins may be blended depending on the purpose. Examples of the resin to be blended include binary copolymers and ternary copolymers composed of polyethylene, ethylene and monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester.

The antifouling film for wallpaper of the present invention has a polypropylene resin layer made of a crystalline polypropylene resin.
The polypropylene resin layer has antifouling properties, and the vinyl chloride layer contains a high-boiling plasticizer by forming the adhesive layer and the polyester resin layer on the polypropylene resin layer. Even if it is, the antifouling film for wallpaper which maintains the strong adhesive force of a polypropylene-type resin layer and a polyester-type resin layer, and is excellent in antifouling property, antiblocking property, and low-temperature adhesiveness is obtained.

The crystalline polypropylene resin constituting the polypropylene resin layer is excellent in embossing followability as well as antifouling properties. Therefore, the embossing characteristics of the crystalline polypropylene resin, the polypropylene resin layer, the polyester resin layer, Due to the synergistic effect of the strong adhesiveness of the polyester resin layer and the vinyl chloride layer of the vinyl chloride wallpaper, even against the surface of the vinyl chloride layer of the foamed vinyl chloride wallpaper, It becomes possible to make it adhere firmly. In addition, the said emboss follow-up property is that a film follows the unevenness etc. which are the designs of wallpaper. When there is no emboss follow-up property, the color may appear partially white, or the surface irregularities may not be sharp.

The crystalline polypropylene resin is not particularly limited. For example, a homopolypropylene resin, a block copolymer of ethylene and propylene, a copolymer of propylene with one or more monomers copolymerizable with ethylene, etc. Is mentioned. When amorphous polypropylene is used, the antifouling property against oily dirt is insufficient.
In the present invention, “crystallinity” means that a raw material pellet or film once heated and melted and then slowly cooled is crystalline, which is a property inherent to the resin.

The polypropylene-based resin layer may be unstretched or stretched, but in terms of embossing followability of the vinyl chloride wallpaper to which the antifouling film for wallpaper of the present invention is adhered, it is unstretched. It is preferable that

In addition, the polypropylene-based resin layer has a flame retardant, an antifungal agent, an antibacterial agent, a moistureproof agent, an antistatic agent, an antiblocking agent, a lubricant, and a filler as long as the properties of the antifouling film for wallpaper of the present invention are not impaired. Additives such as colorants and colorants may be added, and other resins may be blended depending on the purpose.

In the antifouling film for wallpaper of the present invention, the thickness of the polypropylene-based resin layer is not particularly limited, and is appropriately determined in consideration of the performance, price, etc. of the antifouling film for wallpaper, but a preferable lower limit is 1 μm, A preferred upper limit is 100 μm. If it is less than 1 μm, it may be easily damaged by an external impact, and sufficient antifouling properties may not be exhibited. When the thickness exceeds 100 μm, the manufacturing cost increases, and the design such as the design represented on the surface of the vinyl chloride layer is concealed, or the flexibility of the antifouling film for wallpaper of the present invention is reduced. Handling may be reduced.

As a method for producing the antifouling film for wallpaper of the present invention, a method of simultaneously forming each layer by a coextrusion method is preferable. By using such a method, each layer can be formed without using an organic solvent. For example, in co-extrusion using a T-die, any of a feed block method, a multi-manifold method, or a method using these in combination may be used as a lamination method. Specifically, for example, crystalline polypropylene is used as the resin constituting the polypropylene resin layer, maleic acid-modified polyolefin resin is used as the resin constituting the adhesive layer, and polyester is supplied as the resin constituting the polyester resin layer to the extruder. And after extruding into a sheet form with a multilayer die and cooling and fixing with a take-off roll, the method of extending | stretching to 1 axis | shaft or 2 axis | shafts etc. can be used as needed.

By laminating vinyl chloride wallpaper on the antifouling film for wallpaper of the present invention, a wall covering material can be obtained. Such a wall covering is also one aspect of the present invention.

As a vinyl chloride layer of the said vinyl chloride wallpaper, what is used for a well-known vinyl chloride wallpaper can be mentioned, A foam or a non-foam may be sufficient. In particular, in the present invention, even a vinyl chloride wallpaper containing a high-boiling point plasticizer can be suitably used, so that the types of wallpaper that can be used are greatly expanded.
The vinyl chloride layer may be foamed after laminating the wallpaper antifouling film of the present invention. In addition, when printing on the said vinyl chloride layer, printing ink may be used normally. For example, those obtained by mixing and dissolving colorants such as pigments and dyes, dispersants, solvents and the like in acrylic, ethylene-vinyl acetate, urethane, and cellulose resins. The printing can be performed by a known method.

When producing the wall covering material of the present invention, the method for adhering the antifouling film for wallpaper of the present invention to the surface of the vinyl chloride layer is not particularly limited, but it is preferable to adhere by the thermocompression bonding method. Since the thermocompression bonding method does not use organic solvents, solve the problems caused by organic solvents, such as impacts on the natural environment, fire hazards, health effects on workers and waste of resources. Can do.

In addition, the treatment conditions when the antifouling film for wallpaper of the present invention is adhered to the surface of the vinyl chloride layer by the thermocompression bonding method are not particularly limited, and the material constituting the adhesive layer of the antifouling film for wallpaper of the present invention , And its composition and the like. Moreover, when embossing is performed on the vinyl chloride wallpaper, the embossing may be performed simultaneously with the thermocompression bonding of the wallpaper antifouling film of the present invention and the vinyl chloride layer, or may be performed in a subsequent step.

According to the present invention, by using a sulfone group-containing polyester resin as a polyester resin that is a resin constituting the polyester resin layer, a polyester resin layer can be formed by coextrusion molding, and a high-boiling plastic is used. Antifouling film for wallpaper and such antifouling film for wallpaper, which can maintain the adhesive strength between the polypropylene resin layer and the polyester resin layer for a long period of time even when used for vinyl chloride wallpaper containing an agent Can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
As resins constituting the polypropylene resin layer, crystalline polypropylene (manufactured by Prime Polymer, “F707V”), crystalline polypropylene (manufactured by Chisso, “HF3122”), and crystalline polypropylene (manufactured by Chisso, “XFP1498H”) ) Were mixed at a weight ratio of 40: 60: 6, and crystalline polypropylene resin pellets obtained by melt-kneading using a twin-screw kneading extruder were used.
As the resin constituting the adhesive layer, a modified polyolefin resin (manufactured by Mitsui Chemicals, maleic anhydride-modified polyolefin, Admer “SE800”) was used.
As a resin constituting the polyester-based resin layer, 60 parts by weight of a polyester-based resin (manufactured by Eastman Chemical Co., “copolyester 6863”) and a sulfone obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester A mixture of 40 parts by weight of a group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) was used.
These resins were put into an extruder having a barrel temperature of 180 to 280 ° C., extruded from a multilayer die at 250 ° C. into a multilayer sheet having a three-layer structure, and cooled and solidified by a take-up roll at 40 ° C. The obtained antifouling film for wallpaper had a total thickness of 40 μm and had a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Example 2)
A modified polyolefin resin (manufactured by Mitsui Chemicals, maleic anhydride-modified polyolefin resin, Admer “SF731”) is used as the resin constituting the adhesive layer, and a polyester resin (Eastman Chemical) is used as the resin constituting the polyester resin layer. 50 parts by weight of "polypolyester 6763" manufactured by the company and 50 parts by weight of a sulfone group-containing polyethylene terephthalate obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester (intrinsic viscosity: 0.55 dl / g) An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that the mixture was used.
The obtained multilayer antifouling film for wallpaper had a total thickness of 40 μm and consisted of a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Example 3)
A modified polystyrene elastomer (manufactured by Asahi Kasei Chemicals Co., Ltd., maleic anhydride modified SEBS, Tuftec “M1911”) is used as a resin constituting the adhesive layer, and a polyester resin (Eastman Chemical Co., Ltd.) is used as a resin constituting the polyester resin layer. Manufactured by “copolyesterDN010”), 40 parts by weight, and 60 parts by weight of a sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester, An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that this mixture was used.
The obtained antifouling film for wallpaper had a total thickness of 40 μm and had a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

Example 4
As the resin constituting the adhesive layer, an amine-modified styrene-ethylene / butylene-styrene block copolymer (styrene content 30% by weight, MFR 4.0 g / 10 min, specific gravity 0.91, amino group at the end) is used, and polyester type As a resin constituting the resin layer, a sulfone group-containing polyethylene in which 3 mol% of sodium sulfoisophthalic acid is copolymerized with 20 parts by weight of a polyester resin (manufactured by Eastman Chemical Co., Ltd., “copolyester 6863”) and an acid component in the polyester. An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that a mixture with 80 parts by weight of terephthalate (intrinsic viscosity: 0.55 dl / g) was used.
The obtained multilayer antifouling film for wallpaper had a total thickness of 20 μm and consisted of a three-layer structure of polypropylene resin layer (8 μm) / adhesive layer (4 μm) / polyester resin layer (8 μm).

(Example 5)
As a resin constituting the adhesive layer, a modified polyolefin resin (manufactured by Mitsubishi Chemical Corporation, Modic-AP “F515A”) is used. As a resin constituting the polyester resin layer, sodium sulfoisophthalic acid is used with respect to the acid component in the polyester. An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that 3 mol% of a copolymerized sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) was used.
The obtained antifouling film for wallpaper had a total thickness of 20 μm and consisted of a three-layer structure of polypropylene resin layer (12 μm) / adhesive layer (3 μm) / polyester resin layer (5 μm).

(Example 6)
A modified polyolefin resin (manufactured by Mitsubishi Chemical Corporation, Modic-AP “F515A”) is used as the resin constituting the adhesive layer, and a polyester resin (manufactured by Eastman Chemical Co., “copolyester DN010” is used as the resin constituting the polyester resin layer. ”) A mixture of 20 parts by weight and 80 parts by weight of a sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) obtained by copolymerizing 5 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester was used. An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that.
The obtained multilayer antifouling film for wallpaper had a total thickness of 40 μm and consisted of a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Example 7)
As a resin constituting the adhesive layer, a modified polyolefin resin (manufactured by Mitsubishi Chemical Corporation, Modic-AP “F515A”) is used. As a resin constituting the polyester resin layer, sodium sulfoisophthalic acid is used with respect to the acid component in the polyester. An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that 5 mol% copolymerized sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) was used.
The obtained multilayer antifouling film for wallpaper had a total thickness of 40 μm and consisted of a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Example 8)
As a resin constituting the adhesive layer, a modified polyolefin resin (manufactured by Mitsubishi Chemical Corporation, Modic-AP “F515A”) is used. As a resin constituting the polyester resin layer, sodium sulfoisophthalic acid is used with respect to the acid component in the polyester. An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that 10 mol% of a copolymerized sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) was used.
The obtained antifouling film for wallpaper had a total thickness of 20 μm and consisted of a three-layer structure of polypropylene resin layer (12 μm) / adhesive layer (3 μm) / polyester resin layer (5 μm).

(Comparative Example 1)
A modified polyolefin resin (manufactured by Mitsubishi Chemical Corporation, Modic-AP “F515A”) is used as the resin constituting the adhesive layer, and a polyester resin (manufactured by Eastman Chemical Co., “copolyester DN010” is used as the resin constituting the polyester resin layer. ]) Was used in the same manner as in Example 1 except that an antifouling film for wallpaper was prepared.
The obtained antifouling film for wallpaper had a total thickness of 40 μm and had a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Comparative Example 2)
A modified polyolefin resin (manufactured by Mitsui Chemicals, Admer “SE800”) is used as the resin constituting the adhesive layer, and a polyester resin (manufactured by Eastman Chemical Co., “copolyester 6863”) is used as the resin constituting the polyester resin layer. Except for using a mixture of 95 parts by weight and 5 parts by weight of a sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester. An antifouling film for wallpaper was prepared in the same manner as in Example 1.
The obtained antifouling film for wallpaper had a total thickness of 40 μm and had a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Comparative Example 3)
A modified polyolefin resin (manufactured by Mitsui Chemicals, Admer “SF731”) is used as the resin constituting the adhesive layer, and a polyester resin (manufactured by Eastman Chemical Co., “copolyester DN010”) is used as the resin constituting the polyester resin layer. Other than using 90 parts by weight and 10 parts by weight of a sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester Prepared a wallpaper antifouling film in the same manner as in Example 1.
The obtained antifouling film for wallpaper had a total thickness of 40 μm and had a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Comparative Example 4)
A modified polyolefin resin (manufactured by Mitsubishi Chemical Co., Ltd., Modic-AP “F515A”) is used as the resin constituting the adhesive layer, and a polyester resin (manufactured by Eastman Chemical Co., “copolyester 6673” is used as the resin constituting the polyester resin layer. )) A mixture of 80 parts by weight and 20 parts by weight of a sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester was used. An antifouling film for wallpaper was prepared in the same manner as in Example 1 except that.
The obtained multilayer antifouling film for wallpaper had a total thickness of 40 μm and consisted of a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Comparative Example 5)
A modified polyolefin resin (manufactured by Mitsubishi Chemical Co., Ltd., Modic-AP “F515A”) is used as the resin constituting the adhesive layer, and a polyester resin (manufactured by Eastman Chemical Co., “copolyester 6673” is used as the resin constituting the polyester resin layer. ”) A mixture of 70 parts by weight and 30 parts by weight of a sulfone group-containing polyethylene terephthalate (intrinsic viscosity: 0.55 dl / g) obtained by copolymerizing 3 mol% of sodium sulfoisophthalic acid with respect to the acid component in the polyester was used. Except for the above, an antifouling film for wallpaper was prepared in the same manner as in Example 1.
The obtained antifouling film for wallpaper had a total thickness of 40 μm and had a three-layer structure of polypropylene resin layer (16 μm) / adhesive layer (8 μm) / polyester resin layer (16 μm).

(Evaluation)
The adhesion strength and plasticizer resistance of the antifouling films for wallpaper prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated by the following methods. The results are shown in Table 1. Table 1 shows the sulfone group content with respect to the entire resin constituting the polyester resin layer.

(Initial bond strength)
Samples of an appropriate size were cut out from arbitrary 10 points of the antifouling film for wallpaper obtained in Examples and Comparative Examples. Next, a layer containing a polypropylene resin layer is a release layer, a layer containing a polyester resin layer is a release layer, and as shown in FIG. A 100 mm measurement sample was cut out. In the above sample, “vertical” represents the film flow direction, and “horizontal” represents the film width direction. Then, as shown in FIG. 2, the strength when the sample is peeled in the 180 degree direction at a pulling speed of 200 mm / min is measured using a peeling tester (Peeling TESTER HEIDON-17, manufactured by Shinto Kagaku Co., Ltd.). When the strength was 0.2 N / mm or more, the evaluation was ○, and when the strength was less than 0.2 N / mm, the evaluation was ×. In addition, since adhesive strength was very high, when the film was not able to peel at the time of sample preparation (when a sample was not able to be manufactured), it was set as "circle" as "non-peelable". In FIGS. 1 and 2, the adhesive layer is omitted.

(Evaluation of plasticizer resistance at 120 ° C for 20 minutes)
Samples of an appropriate size were cut out from arbitrary 10 points of the antifouling film for wallpaper obtained in Examples and Comparative Examples. Next, the polyester resin layer of the wallpaper antifouling film and the vinyl chloride layer of the vinyl chloride wallpaper are overlapped, and the temperature is 120 ° C. and the pressure is 26 kg with a press machine (“MHPC-V-50-450” manufactured by Meiki Seisakusho). / Cm ² , and pressed for 20 minutes. A layer containing the polypropylene resin layer of the sample thus obtained was used as a release layer, a layer containing a polyester resin layer was used as a release layer, and a part of the end of the film was peeled off as shown in FIG. Thereafter, a measurement sample having a length of 10 mm and a width of 100 mm was cut out. In the above sample, “vertical” represents the film flow direction, and “horizontal” represents the film width direction. Then, as shown in FIG. 4, the strength when the sample is peeled in the 180 degree direction at a pulling speed of 200 mm / min is measured using a peeling tester (Peeling TESTER HEIDON-17, manufactured by Shinto Kagaku Co., Ltd.). When the strength was 0.1 N / mm or more, the evaluation was ○, and when the strength was less than 0.1 N / mm, the evaluation was ×. In addition, since adhesive strength was very high, when the film was not able to peel at the time of sample preparation (when a sample was not able to be manufactured), it was set as "circle" as "non-peelable". 3 and 4, the adhesive layer is omitted.

(Evaluation of plasticizer resistance at 120 ° C for 30 minutes)
Samples of an appropriate size were cut out from arbitrary 10 points of the antifouling film for wallpaper obtained in Examples and Comparative Examples. Next, the polyester resin layer of the wallpaper antifouling film and the vinyl chloride layer of the vinyl chloride wallpaper are overlapped, and the temperature is 120 ° C. and the pressure is 26 kg with a press machine (“MHPC-V-50-450” manufactured by Meiki Seisakusho). / Cm ² , pressed for 30 minutes. In the same manner as in the case of (plasticizer resistance evaluation at 120 ° C. for 20 minutes), the strength obtained when the sample was peeled in the direction of 180 degrees was measured as a peeling tester (Peeling TESTER HEIDON- 17, manufactured by Shinto Kagaku Co., Ltd.), when the strength was 0.1 N / mm or more, the evaluation was ○, and when the strength was less than 0.1 N / mm, the evaluation was ×. In addition, since adhesive strength was very high, when the film was not able to peel at the time of sample preparation (when a sample was not able to be manufactured), it was set as "circle" as "non-peelable".

The antifouling films for wallpaper obtained in Examples 1 to 8 had sufficient adhesive strength in both cases of initial adhesive strength and plasticizer resistance. This means that even when the plasticizer bleeds with time, the polyester-based resin layer and the polypropylene-based resin layer do not peel off unless a strong force is applied. It can be said that the adhesive strength between the polyester resin layer and the polypropylene resin layer in the wallpaper antifouling film is practically sufficient. On the other hand, the wallpaper antifouling film obtained in the comparative example was found to have a remarkable decrease in adhesive strength over time and a low plasticizer resistance.

According to the present invention, it can be produced by a method such as coextrusion molding without using an organic solvent, and even when a vinyl chloride layer contains a high boiling point plasticizer, it is powerful. It is possible to provide an antifouling film for wall paper and a wall covering material that maintains adhesive strength and is excellent in antifouling properties and antiblocking properties.

It is a figure which shows the peeling state of the film in initial stage adhesive strength evaluation. It is a figure which shows the adhesive strength measurement state of the film in initial stage adhesive strength evaluation. It is a figure which shows the peeling state of the film in plasticizer resistance evaluation. It is a figure which shows the adhesive strength measurement state of the film in plasticizer resistance evaluation.

Explanation of symbols

1 Polypropylene resin layer 2 Polyester resin layer 3 Vinyl chloride wallpaper

Claims (2)

An antifouling film for wallpaper used for vinyl chloride wallpaper containing a high-boiling plasticizer,
A polypropylene resin layer composed of a crystalline polypropylene-based resin, a polyester resin layer having a sulfonic group-containing polyester resin is laminated through an adhesive layer,
The adhesive layer contains a modified styrene elastomer and / or a modified polyolefin resin,
The antifouling film for wallpaper characterized by containing 1.2-30 mol% of sulfone groups with respect to the whole resin which comprises the said polyester-type resin layer. Wall coverings, characterized in that the wallpaper antifoulant film of claim 1 Symbol mounting and consisting of a vinyl chloride wallpaper.

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