JP2017179031A - Resin composition, manufacturing method of resin sheet, manufacturing method of laminate sheet and manufacturing method of foam wallpaper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of crosslinking by heat or a moisture content, preventing a gel from generating even at extrusion molding, a manufacturing method of a resin sheet, a manufacturing method of a laminate sheet and a manufacturing method of a foam wallpaper, using the resin composition.SOLUTION: A resin composition is for forming a foam resin layer of a foam wallpaper including a base material and the foam resin layer disposed on the base material. The resin composition includes a foaming agent, a filler, and a resin content including a silane crosslinkable resin and a polyolefin resin. If a melt flow rate of all components other than the silane crosslinkable resin in the resin composition is N, N is 1 to 50. The resin composition includes the silane crosslinkable resin having a melt flow rate of 0.5 N to 1.5 N.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a method for producing a resin sheet, a method for producing a laminated sheet, and a method for producing foamed wallpaper. In more detail, this invention relates to the manufacturing method of the resin composition which can be utilized for the wall surface decoration etc. of buildings, such as a detached house, an apartment house, a store, and an office building, and a resin sheet, a lamination sheet, and a foam wallpaper.

  As wallpaper used for wall decoration of buildings, vinyl chloride wallpaper in which a resin layer of vinyl chloride resin is provided on a paper base material is widely used. In recent years, in consideration of the environment, a halogen-free resin such as an ethylene-vinyl acetate copolymer has been used (for example, see Patent Documents 1 and 2 below).

  As a method for producing these foamed wallpaper, first, a resin composition containing a foaming agent is melt-extruded coated and laminated on a base material, or separately sheeted by a T-die extrusion method, and later dry laminated or A laminated sheet in which a resin sheet is provided on a substrate is obtained by bonding the substrates together by thermal lamination. Then, if necessary, the resin sheet having the surface printed thereon is heated to decompose and foam the foaming agent. These methods are advantageous in terms of production efficiency as compared with a method of applying and drying a resin composition on a substrate.

  The resin composition for foamed wallpaper is required to have a satisfactory foaming state in which a sufficient foaming ratio is obtained when the formed resin sheet is foamed and the outgassing is not noticeable. Therefore, the viscosity is adjusted to be suitable for foaming by performing a crosslinking treatment with an electron beam or the like after film formation (see, for example, Patent Document 3 below). However, in the electron beam irradiation, in addition to performance problems such as yellowing the paper base material, there are also problems such as an expensive electron beam irradiation device.

Japanese Patent Laid-Open No. 6-47875 JP 2001-347611 A Japanese Patent No. 3923969

  The present inventors have studied a resin sheet that can be cross-linked by means other than electron beam. As a result, the resin sheet containing a silane cross-linkable resin can be sufficiently cross-linked by heat and moisture, and a good foamed state is obtained. It was found that it can be formed. On the other hand, the inventors have also found that gels may be generated when a resin composition containing a silane crosslinkable resin is extruded.

  The present invention has been made in view of the above circumstances, and uses a resin composition that can be cross-linked by heat and moisture and hardly generates a gel even when extruded, and the resin composition. It aims at providing the manufacturing method of a resin sheet, the manufacturing method of a lamination sheet, and the manufacturing method of foam wallpaper.

  That is, the present invention is a resin composition for forming a foamed resin layer of a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, the foaming agent and a filler , A resin component containing a silane crosslinkable resin and a polyolefin resin, and when N is a melt flow rate of all components other than the silane crosslinkable resin in the resin composition, N is 1 to 50, A resin composition comprising a silane crosslinkable resin having a melt flow rate of 0.5 N to 1.5 N.

  Since the resin composition of the present invention has the above-described configuration, it can be cross-linked by heat or moisture, and can hardly generate a gel even when it is extruded. That is, according to the resin composition of the present invention, a resin sheet having a sufficiently small gel and capable of crosslinking by heat or moisture can be obtained by extrusion molding. The reason why such an effect is obtained is that the above-mentioned matrix having a specific melt flow rate contains a silane crosslinkable resin having a flow rate in which a flow rate ratio to the matrix is within a specific numerical range, thereby allowing silane crosslinking. The present inventors speculate that the compatibility between the functional resin and the components other than the silane crosslinkable resin is improved, and the silane crosslinking reaction is sufficiently prevented from proceeding locally around the silane crosslinkable resin. To do.

  Moreover, this invention provides the manufacturing method of a resin sheet provided with the resin sheet formation process which forms a resin sheet by extruding the resin composition which concerns on the said invention.

  This invention also provides the manufacturing method of a lamination sheet provided with the lamination sheet formation process which laminates the resin sheet obtained by the manufacturing method of the resin sheet which concerns on the said invention on the base material, and obtains a lamination sheet.

  The laminated sheet manufacturing method includes a crosslinking step of crosslinking a part or all of the resin contained in the resin sheet before or during lamination on the substrate, or the resin content contained in the resin sheet in the laminated sheet. You may further provide the bridge | crosslinking process which bridge | crosslinks part or all.

  The crosslinking is preferably performed using superheated steam. By performing the crosslinking reaction using superheated steam, the reaction efficiency of the crosslinking reaction can be increased, and a laminated sheet having desired characteristics can be efficiently produced.

  Moreover, this invention is a manufacturing method of the foam wallpaper provided with a base material and the foamed resin layer provided on this base material, Comprising: The laminated sheet obtained by the manufacturing method of the laminated sheet which concerns on the said invention There is provided a method for producing a foamed wallpaper, comprising a foaming step of forming a foamed resin layer by foaming a foaming agent contained in.

  According to the present invention, a resin composition that can be cross-linked by heat and moisture and hardly generates a gel even when extruded, a method for producing a resin sheet using the resin composition, and a laminated sheet A manufacturing method and a manufacturing method of foam wallpaper can be provided.

[Resin composition]
The resin composition according to the present embodiment is a resin composition for forming a foamed resin layer of foamed wallpaper comprising a base material and a foamed resin layer provided on the base material, and a foaming agent And a filler and a resin component.

  Hereinafter, each component contained in the resin composition will be described in more detail.

<Foaming agent>
Examples of the foaming agent according to this embodiment include azo foaming agents such as azodicarbonamide, hydrazide foaming agents such as p-toluenesulfonyl hydrazide, and nitroso foaming agents such as N, N′-dinitrosopentamethylenetetramine. These can be used, and these can be used alone or in combination of two or more. The content of the foaming agent is not particularly limited, but the total amount is preferably 2 to 30% by mass based on the total amount of the resin composition. When the content of the foaming agent is within the above range, yellowing that occurs when the foaming agent remains in the foamed wallpaper after foaming can be suppressed, and a foamed wallpaper that is favorable in terms of compression recovery and feel can be produced. .

  As the foaming agent, for example, commercially available products such as VINYHALL AC # 3C-K2 (manufactured by Eiwa Kasei Co., Ltd., azodicarbonamide-based foaming agent) can be used.

<Filler>
Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include calcium carbonate and titanium dioxide. These can be used alone or in combination of two or more. Examples of the organic filler include melamine cyanurate, polytetrafluoroethylene (PTFE), wood flour, cellulose, and derivatives thereof. These may be used alone or in combination of two or more. it can.

  The content of the filler is not particularly limited, but the total amount is preferably 10 to 70% by mass based on the total amount of the resin composition. Reasons for adding the filler include securing the concealing property of the foam wallpaper, reducing the combustion calories per unit area, reducing the production cost by increasing the bulk, etc., but the filler content is the total amount of the resin composition. When it is 10 to 70% by mass as a reference, it is possible to produce a foam wallpaper having a low production calorie and a low calorie calorie while ensuring good concealment as a foam wallpaper.

  Although it does not restrict | limit especially as an average particle diameter of a filler, For example, it is preferable that it is 0.1-5.0 micrometers, and it is more preferable that it is 0.2-3.0 micrometers. In the present specification, the average particle diameter means a value obtained by the air permeation method.

  Examples of the filler include commercially available products such as Softon 1000 (Calcium Carbonate, manufactured by Bihoku Flour Industries Co., Ltd.), Taipei CR-60-2, and Taipei CR-60 (above, Ishihara Sangyo Co., Ltd., titanium dioxide). Can be used.

<Resin content>
The resin component according to this embodiment contains a silane crosslinkable resin and a polyolefin resin.

  As the silane crosslinkable resin, for example, a silane crosslinkable polyolefin resin or the like can be used. Examples of the silane crosslinkable polyolefin resin include a resin in which a hydrolyzable silyl group is mainly introduced into a side chain in a polyolefin polymer as a matrix. Examples of such a resin include a resin in which a hydrolyzable silyl group is mainly introduced into a side chain in a polymer such as a low density polyethylene type, a high density polyethylene type, an ethylene-vinyl acetate copolymer system, or a polypropylene type. . Crosslinking is carried out by hydrolysis of substituted silyl groups. In addition, the polyolefin resin which this silyl group is located in the terminal may be contained.

  Silane crosslinkable polyolefin resin is a method in which a monomer of polyolefin polymer and a silane compound having an ethylenically unsaturated group or epoxy group are randomly copolymerized in a container, or a peroxide in a polyolefin polymer melt. Can be obtained by a method such as graft copolymerization of the above silane compound. Here, the polyolefin polymer as a matrix can be used alone or in combination of two or more of ethylene homopolymers described later or copolymers of ethylene and other olefins. Further, the base polyolefin-based resin may be used in combination with the polyolefin-based resin and a resin different from the polyolefin-based resin as long as mixing or dispersion of the resins is allowed. The degree of mixing or dispersion varies greatly depending on the type of extruder used, and an appropriate compatibilizer can be used. Therefore, the combined resins cannot be generally classified, but are preferably the same type of resins.

  Examples of the silane compound having an ethylenically unsaturated group include a silane compound having a vinyl group, a silane compound having an acryloyl group, and a silane compound having a methacryloyl group. Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane, vinyltriphenoxysilane, vinyltribenzyloxy. Examples include silane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinyltripropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. Examples of the silane compound having an acryloyl group include 3-acryloxypropyltrimethoxysilane. Examples of the silane compound having a methacryloyl group include 3-methacryloxypropylmethyldimethoxysilane.

  Examples of the silane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.

  As the silane crosslinkable resin, for example, a commercially available product such as Linklon XCF710N (manufactured by Mitsubishi Chemical Corporation) can be used.

  The content of the silane crosslinkable resin in the resin composition according to the present embodiment is not particularly limited, but from the viewpoint of achieving both a high level of molding stability and crosslinkability such as generation of gel and surface roughness. Based on the total amount of the resin composition, it is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and further preferably 15 to 30% by mass.

  Examples of the polyolefin-based resin include an ethylene homopolymer, a copolymer of ethylene and another olefin, and the like. Ethylene homopolymers and copolymers of ethylene and other olefins are non-polar non-halogen thermoplastic resins, and by using these, ethylene-methyl methacrylate copolymer resins, ethylene-vinyl acetate copolymers Compared to the case of using a resin and a polar resin such as an ionomer resin, an increase in viscosity when the amount of filler is increased can be suppressed, so that high-quality wallpaper can be stably produced.

  Examples of the ethylene homopolymer include low density polyethylene synthesized by a high pressure method, high density polyethylene not containing a comonomer synthesized by a medium pressure method, and the like. Among these, low density polyethylene is preferable.

Low density polyethylene, for example, those having a density in the range of 0.91 g / cm ³ or more 0.94 g / cm ³ or less. The density of low-density polyethylene is preferably not 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.92 g / cm ³ or more 0.93 g / cm ³ or less. Although it does not restrict | limit especially about the molecular weight of a low density polyethylene, melting | fusing point, etc., About melting | fusing point, 50 to 140 degreeC is preferable and 60 to 110 degreeC is more preferable. When the melting point is 140 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent can be prevented from being decomposed during molding. On the other hand, if the melting point is 50 ° C. or higher, thermal durability in actual use can be easily obtained.

  As low-density polyethylene, for example, commercially available products such as Novatec LD LC802A, Novatec LD LC604, Novatec LD LC600A (manufactured by Nippon Polyethylene Co., Ltd.), Ube Polyethylene J2516 (produced by Ube Maruzen Polyethylene Co., Ltd.) can be used.

High density polyethylene, for example, those density is largely 0.960 g / cm ³ or less in the range from 0.940 g / cm ^3. The density of high-density polyethylene is preferably at 0.945 g / cm ³ or more 0.955 g / cm ³ or less. Although it does not restrict | limit especially about the molecular weight of a high density polyethylene, melting | fusing point, etc., About melting | fusing point, 120 to 150 degreeC is preferable and 130 to 150 degreeC is more preferable. When the melting point is 150 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent can be prevented from being decomposed during molding. On the other hand, if the melting point is 120 ° C. or higher, thermal durability in actual use can be easily obtained.

  As the high-density polyethylene, for example, commercially available products such as Novatec HD HJ490 (manufactured by Nippon Polyethylene Co., Ltd.), M6910 (manufactured by Keiyo Polyethylene Co., Ltd.), Suntec J311 (manufactured by Asahi Kasei Chemicals Corporation) can be used.

  Examples of the copolymer of ethylene and other olefins include linear low density polyethylene, ultra-low density polyethylene, high density polyethylene obtained by copolymerization with a comonomer, and the like. Alternatively, two or more kinds can be used in combination. Among these, ultra-low density polyethylene is preferable.

The ultra low density polyethylene, for example, those having a density in the range of less than 0.85 g / cm ³ or more 0.91 g / cm ^3. The density of the ultra-low density polyethylene is preferably 0.86 g / cm ³ or more and 0.90 g / cm ³ or less, more preferably 0.87 g / cm ³ or more and 0.90 g / cm ³ or less, and still more preferably 0.87 g / cm ³ or more and 0.90 g / cm ³ or less, particularly preferably 0.88 g / cm ³ or more and 0.90 g / cm ³ or less, and most preferably 0.89 g / cm ³ or more and 0.90 g or less. / Cm ³ or less. The molecular weight and melting point of the ultra-low density polyethylene are not particularly limited, but the melting point is preferably 50 to 100 ° C, more preferably 55 to 90 ° C. If the melting point is 100 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent can be prevented from being decomposed during molding. On the other hand, if the melting point is 50 ° C. or higher, thermal durability in actual use can be easily obtained.

  Examples of the ultra-low density polyethylene include Tafmer DF140, DF940, DF7350 (Mitsui Chemical Co., Ltd.), Kernel KJ640T (Nihon Polyethylene Co., Ltd.), Excellen FX CX5508 (Sumitomo Chemical Co., Ltd.), Engage 8400/8407. Commercial products such as Dow Chemical Co., Evolue P SP90100 (Prime Polymer Co., Ltd.) can be used.

  The content of the polyolefin resin in the resin component according to this embodiment is not particularly limited, but the total amount is preferably 10 to 80% by mass based on the total amount of the resin composition, and is preferably 20 to 70% by mass. % Is more preferable, and 40 to 50% by mass is even more preferable.

  Moreover, it is preferable that the resin part which concerns on this embodiment contains an ultra-low density polyethylene among the said polyolefin resin. In this case, the content of the ultra-low density polyethylene is preferably 10 to 90% by mass, more preferably 30 to 90% by mass, and 30 to 80% by mass based on the total amount of the polyolefin resin. More preferably.

  In addition to the ultra-low density polyethylene as the polyolefin resin, the resin component according to the present embodiment further preferably includes low density polyethylene and / or high density polyethylene, and particularly preferably includes low density polyethylene. In this case, the total content of low-density polyethylene and / or high-density polyethylene is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total amount of polyolefin resin. More preferably, it is 40-60 mass%.

  Moreover, the resin composition according to the present embodiment may be colored by adding a pigment or the like as necessary. Coloring by adding a pigment may be transparent, translucent, or opaque. Examples of the pigment include inorganic pigments such as iron oxide and carbon black, and organic pigments such as aniline black and phthalocyanine blue.

  The addition amount of the pigment is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the total amount of the resin composition.

  Moreover, well-known additives, such as a flame retardant, a cell regulator, a stabilizer, a lubricant, a foaming aid, a silane crosslinking aid, can be used for a resin composition as needed.

  Examples of the flame retardant include metal oxide flame retardants such as magnesium hydroxide and aluminum hydroxide, phosphorus flame retardants such as phosphate ester, and bromine flame retardants such as tetrabromobisphenol A.

  Examples of the cell modifier include acrylic ester resins and methacrylic ester resins.

  Examples of the stabilizer include amine-based antioxidants, radical scavengers such as hindered amine-based light stabilizers, peroxide-based and sulfur-based peroxide decomposers, and heat-based stabilizers such as phenol-based antioxidants. It is done.

  Examples of the lubricant include fatty acid series such as stearic acid and lauric acid, fatty acid amide series such as stearic acid amide and oleic acid amide, and metal soap type lubricants such as zinc stearate, calcium laurate, and zinc octylate. . As the lubricant, for example, commercially available products such as ADK STAB AP-546 and ADK STAB OF-101 (above, manufactured by ADEKA Corporation) can be used.

  Examples of the foaming aid include urea, zinc chloride, zinc oxide and the like in addition to the above metal soap lubricant.

  Examples of the silane crosslinking aid include tin-based crosslinking aids such as dioctyltin dilaurate.

  In the resin composition according to the present embodiment, N is 1 to 50, where N is the melt flow rate of all components other than the silane crosslinkable resin in the resin composition (hereinafter also referred to as MFR), And a silane crosslinkable resin having an MFR of 0.5N to 1.5N.

  By satisfy | filling said conditions, the resin composition which concerns on this embodiment can be bridge | crosslinked with a heat | fever and a water | moisture content, and can become a thing which a gel does not generate | occur | produce easily even when it is extruded.

For the MFR (N) of all components other than the silane crosslinkable resin in the resin composition, for example, a mixture obtained by mixing each component other than the silane crosslinkable resin contained in the resin composition is melt indexer D4003 (Nippon Dynisco Corporation). The time required for the piston to move a predetermined distance can be measured using the following formula:
MFR = average cross-sectional area of piston and cylinder (cm ² ) × seconds of reference time 600 (s) × predetermined piston moving distance (cm) × melting density at test temperature (g / cm ³ ) ÷ average of measurement time Value (s)

  The N needs to be 1 to 50, preferably 10 to 50, more preferably 10 to 30, and still more preferably 20 to 30. If N is 1 or more, shear heat generated during molding can be suppressed, the processing temperature can be easily controlled, and the foaming agent can be prevented from being decomposed during molding. On the other hand, if N is 50 or less, the mechanical strength of the produced foamed wallpaper is maintained, and a layer excellent in workability and durability is easily formed.

  The N can be adjusted by, for example, the particle size and blending amount of the filler, the selection of the polyolefin resin, and the like.

  Whether or not the silane crosslinkable resin has an MFR of 0.5N to 1.5N is determined for each silane crosslinkable resin when there are two or more silane crosslinkable resins and silane crosslinkable resins to be blended. This can be confirmed by measuring the melt flow rate.

The MFR of the silane crosslinkable resin is obtained by, for example, measuring the time required for the piston to move a predetermined distance from the pellet of the silane crosslinkable resin using a melt indexer D4003 (manufactured by Nippon Dinisco Co., Ltd.). More measurable.
MFR = average cross-sectional area of piston and cylinder (cm ² ) × seconds of reference time 600 (s) × predetermined piston moving distance (cm) × melting density at test temperature (g / cm ³ ) ÷ average of measurement time Value (s)

  By blending a silane crosslinkable resin having an MFR of 0.5N to 1.5N, sufficient crosslinkability can be imparted while suppressing the generation of gel. From such a viewpoint, the MFR of the silane crosslinkable resin is preferably 0.5N to 1.5N, more preferably 0.7N to 1.3N, and 0.9N to 1.1N. Is more preferable.

  The MFR of the silane crosslinkable resin is not particularly limited as long as it satisfies the above 0.5N to 1.5N, but is preferably 0.7N to 1.3N, and is preferably 0.9N to 1.1N. It is more preferable. If MFR of silane crosslinkable resin is 0.5N-1.5N, compatibility with components other than silane crosslinkable resin will become good, and there exists a tendency which suppresses generation | occurrence | production of a gel.

  The MFR of the silane crosslinkable resin can be adjusted, for example, by a method such as appropriately selecting the MFR of the polyolefin-based polymer as the matrix.

  Moreover, the silane crosslinkable resin which concerns on this embodiment can contain silane crosslinkable resins other than the silane crosslinkable resin which has MFR of 0.5N-1.5N in the range which does not impair the effect of this invention. In the silane crosslinkable resin according to this embodiment, the content of the silane crosslinkable resin other than the silane crosslinkable resin having an MFR of 0.5N to 1.5N is 5% by mass or less based on the total amount of the silane crosslinkable resin. It is preferable that no silane crosslinkable resin other than the silane crosslinkable resin having an MFR of 0.5N to 1.5N is included.

[Production method of resin sheet]
The manufacturing method of the resin sheet which concerns on this embodiment is equipped with the resin sheet formation process which forms a resin sheet by extruding the resin composition which concerns on this embodiment mentioned above.

  Examples of the extrusion molding method include extrusion molding such as a T-die extrusion method, a T-die extrusion simultaneous lamination method, a T-die extrusion tandem lamination method, a circular die extrusion method, and a circular die inflation extrusion method.

  In addition to extrusion molding, the resin sheet can be produced by known molding methods such as injection molding, press molding, blow molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding, and the like.

  The resin composition can be used by appropriately pelletizing each component after melting, kneading and dispersing with an extruder. The extruder may be a single-screw extruder or a twin-screw extruder, but a twin-screw extruder is preferable in view of the influence on productivity and quality.

  Extrusion conditions include an extrusion temperature of 100 to 160 ° C. and an extrusion pressure of 2 to 50 MPa. The extrusion temperature is preferably 110 to 150 ° C., and preferably 120 to 140 ° C. from the viewpoint of setting the resin component to the melting point or higher while suppressing the decomposition of the foaming agent component. From the viewpoint of extrusion stability, the extrusion pressure is preferably 3 to 40 MPa, more preferably 3 to 30 MPa.

  Although the thickness of a resin sheet can be suitably set according to a use, if it is a foam wallpaper application, for example, it can be 50-200 micrometers.

  The manufacturing method of the resin sheet which concerns on this embodiment may further be equipped with the bridge | crosslinking process which bridge | crosslinks part or all of the resin part contained in the resin sheet mentioned above. Examples of the cross-linking treatment include superheated steam treatment, water cross-linking treatment, etc., from the viewpoint that the reaction efficiency of the cross-linking reaction can be increased, and a resin sheet having desired characteristics can be efficiently produced. Steam treatment is preferred.

  Examples of the superheated steam treatment include a method in which superheated steam (also referred to as superheated steam) is treated in an environment of 130 to 280 ° C. for 20 seconds to 15 minutes. The superheated steam treatment includes, for example, a method in which a resin sheet is arranged in a superheated steam atmosphere and the superheated steam is brought into contact with the resin sheet. Moreover, as a method of water-crosslinking, a method of water-crosslinking by curing for 1 day to 1 month in a temperature range of 40 to 70 ° C. in an environment of humidity of 60% or more is specifically mentioned. A method of curing and water-crosslinking in an environment of a constant temperature and humidity chamber of%.

  The crosslinking treatment of the resin sheet may be performed on a molded resin composition or may be performed after forming a laminated sheet described later.

[Production method of laminated sheet]
The manufacturing method of the lamination sheet which concerns on this embodiment is equipped with the lamination sheet formation process of laminating the resin sheet obtained at the said resin sheet formation process on a base material, and obtaining a lamination sheet.

  The laminating method is not particularly limited, and examples thereof include a method in which a resin sheet and a base material are subjected to thermocompression bonding using a hot press machine, a method in which pressure bonding is performed using superheated steam, and the like. According to the method of performing pressure bonding using superheated steam, it becomes possible to laminate on the base material while maintaining the molten state of the surface of the resin sheet by superheated steam, and the leveling effect makes it possible to laminate the surface of the base material to be adhered. It is possible to suppress the unevenness from being transferred to the resin sheet. Moreover, when a resin sheet contains a silane crosslinkable resin, a silane crosslinkable resin can be bridge | crosslinked efficiently by superheated steam.

The base material is not particularly limited as long as it is usually used as a paper base material such as a conventional backing paper for wallpaper. As such a substrate, for example, a pulp-based flame retardant paper impregnated with a water-soluble flame retardant such as guanidine sulfamate or guanidine phosphate, or an inorganic agent such as magnesium carbonate, aluminum hydroxide, magnesium hydroxide or the like. Examples include mixed paper. These weighings may be 50 to 300 g / m ² or 60 to 160 g / m ² .

  Further, from the viewpoint of improving the adhesion between the base material and the resin sheet, the surface on the side of the base material where the resin sheet is provided is subjected to easy adhesion processing such as corona discharge treatment, plasma treatment, ozone treatment, etc. Alternatively, an easy adhesion treatment layer formed from an acrylic-butyl copolymer, polyurethane composed of isocyanate and polyol, or the like may be provided.

  The method for producing a laminated sheet according to the present embodiment includes a crosslinking step for crosslinking a part or all of the resin contained in the resin sheet before or during lamination on the substrate, or the resin sheet in the laminated sheet. A cross-linking step of cross-linking a part or all of the resin component may be further provided. The crosslinking treatment can be the same as the method described in the method for producing the resin sheet. When the resin sheet contains a silane crosslinkable resin, lamination and crosslinking of the silane crosslinkable resin can be performed simultaneously with superheated steam.

[Method for producing foam wallpaper]
The foam wallpaper according to the present embodiment includes a base material and a foamed resin layer provided on the base material. Such a foam wallpaper includes a foaming step in which a foamed resin layer is formed by foaming a foaming agent contained in the laminate sheet obtained in the laminate sheet forming step.

  Foaming of the foaming agent can be performed by heating the resin sheet. The heating condition can be appropriately set depending on the components constituting the resin sheet, and is not particularly limited, but is preferably heated at 160 to 280 ° C. for 10 to 120 seconds, and at 220 to 240 ° C. for 20 to 40 seconds. Heating is more preferable, and heating at 220 ° C. for 40 seconds is further preferable.

  Furthermore, in the manufacturing method of the foam wallpaper which concerns on this embodiment, the uneven | corrugated shape formation process which provides an uneven | corrugated shape in the surface on the opposite side to the base material of a foamed resin layer may be provided. An uneven | corrugated shape formation process can be equipped after the said foaming process, for example. The method for providing the uneven shape is not particularly limited. For example, by using heat at the time of heating and foaming, the surface side is a cooling embossing roll, the base material side is a rubber roll, Examples of the method include forming a concavo-convex shape on the surface by niping (embossing) and cooling. The uneven shape is not particularly limited, and examples thereof include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texturer, a satin texture, a grain texture, a hairline, and a single line groove. These can be appropriately selected according to the purpose, and a plurality of them may be combined.

  The method for producing foam wallpaper according to the present embodiment may include a printing step of providing a pattern layer and a surface protective layer. The pattern layer and the surface protective layer can be appropriately provided using known materials. If the object of the present invention can be achieved, the pattern layer and the surface protective layer may not be provided. The pattern layer and the surface protective layer can be provided using a known printing technique such as gravure coating. In addition, a printing process can be provided before the said foaming process, for example. That is, the pattern layer and the surface protective layer can be provided before foaming the foaming agent.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

[Production of resin sheet]
(Examples 1-4, Comparative Examples 1-6)
Using a T-die having a coat hanger-type manifold, a flight screw with a dull mage of screw diameter (D) 15 mm, L / D (screw length divided by screw diameter) = 25 is shown in Table 1. A resin composition having a composition (numerical values other than N value, 0.5N value, and 1.5N value in the table indicate parts by mass) was formed at an extrusion temperature of 115 ° C. and a thickness of 100 μm to obtain a resin sheet. . At this time, the extrusion time of the resin composition was 60 minutes.

  The following materials were used for each component shown in Table 1.

[Low density polyethylene]
Polyolefin resin A: Novatec LD LC802A (manufactured by Nippon Polyethylene Co., Ltd., trade name, density = 0.917 g / cm ³ , MFR = 27)
Polyolefin resin B: Novatec LD LC600A (manufactured by Nippon Polyethylene Co., Ltd., trade name, density = 0.918 g / cm ³ , MFR = 7)

[Ultra low density polyethylene]
Polyolefin resin C: Kernel KJ640T (manufactured by Nippon Polyethylene Co., Ltd., trade name, density = 0.880 g / cm ³ , MFR = 30)

[Calcium carbonate]
Filler A: Softon 1000 (Bihoku Powder Chemical Co., Ltd., trade name, average particle size 2.2 μm)

[titanium dioxide]
Filler B: Taipei CR-60 (Ishihara Sangyo Co., Ltd., trade name, average particle size 0.21 μm)

Foaming agent: VINYHALL AC # 3C-K2 (manufactured by Eiwa Kasei Kogyo Co., Ltd., trade name, azodicarbonamide foaming agent)

Foaming aid: ADK STAB OF-101 (manufactured by ADEKA Corporation, trade name, zinc-based foaming aid)

Cross-linking catalyst: Low-density polyethylene base, cross-linking catalyst with MFR = 25 (Mitsubishi Chemical Corporation)

[Silane crosslinkable resin]
Silane crosslinkable resin A: low density polyethylene base, MFR = 8, gel fraction = 66% silane crosslinkable resin Silane crosslinkable resin B: low density polyethylene base, MFR = 12, gel fraction = 58% Silane crosslinkable resin Silane crosslinkable resin C: low density polyethylene base, MFR = 15, gel fraction = 53% silane crosslinkable resin Silane crosslinkable resin D: low density polyethylene base, MFR = 25, gel fraction = Silane crosslinkable resin 43% Silane crosslinkable resin E: Low density polyethylene base, MFR = 3, Gel fraction = 73% Silane crosslinkable resin Silane crosslinkable resin F: Low density polyethylene base, MFR = 50 Silane crosslinkable resin with gel fraction = 64% Silane crosslinkable resin G: low density polyethylene base, MFR = 90, gel fraction = 57% Run crosslinking resin silane crosslinkable resin H: low-density polyethylene-based, MFR = 110, silane crosslinkable resin is a gel fraction = 47%

[Measurement of MFR]
A silane crosslinkable resin pellet contained in the resin composition and a pellet obtained by mixing components other than the silane crosslinkable resin contained in the resin composition were prepared. The MFR of these pellets was measured according to the following procedure.
The melt indexer D4003 (manufactured by Nippon Dynisco Corporation, trade name) was used to measure the time for which the piston moved a predetermined distance, and the MFR was measured from the following calculation formula.
MFR = average cross-sectional area of piston and cylinder (cm ² ) × seconds of reference time 600 (s) × predetermined piston moving distance (cm) × melting density at test temperature (g / cm ³ ) ÷ average of measurement time Value (s)

[Evaluation of resin sheet]
About the resin sheet produced in the Example and the comparative example, the number of gels was measured by visual observation. The results are shown in Table 2.

＊１：ゲル多数により計測不可

* 1: Cannot be measured due to many gels

[Production of foam wallpaper]
The resin sheet formed as described above is placed on the backing paper (KJ Special Paper, WK-6651HT, weight 65 g / m ² ), and pressed for 2 minutes under a condition of a press pressure of 5 MPa with a hot press machine heated at 110 ° C. And laminated to obtain a laminated sheet.

Furthermore, after corona discharge treatment is applied to the resin sheet side surface, a pattern is printed at 1 g / m ² using a water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., Hydrick WP) with a gravure printing machine, and gravure coating A matte surface coating agent (Nissin Chemical Industry Co., Ltd., Vinyl Blanc 089) was applied at 2 g / m ² using a machine (Kurashita Boseki Co., Ltd., GP-10) to prepare a raw material before cross-linking.

  Each of the raw materials before cross-linking was put into a superheated steam furnace having a steam temperature of 140 ° C. and a superheated steam amount of 60 kg / hour, and sprayed with superheated steam for 5 minutes to crosslink the resin component to obtain a cross-linked laminated sheet. .

  Each laminated sheet obtained above was heated in an oven at 220 ° C. for 40 seconds to foam the foaming agent to produce a foam wallpaper. The performance evaluation shown below was performed about the produced foam wallpaper. Table 3 shows the results of performance evaluation of each foamed wallpaper. All of the foamed wallpapers had good foaming properties and good bubble states, and were of a quality having no practical problem.

<Foaming ratio>
The cross-section was taken out with a razor blade, and observed and measured with a microscope (manufactured by Keyence Corporation: VHX-600 (trade name)).

<Bubble state>
The cell state was cross-sectioned with a razor blade, and the presence or absence of outgassing on the surface was visually confirmed. In addition, when the shape of the cell was uniform to some extent, “◯” was evaluated, and when the cell size was different and a huge cell was seen, “×” was evaluated. If it is “◯”, it can be said that the bubble state is good.

Claims (6)

A resin composition for forming the foamed resin layer of a foam wallpaper comprising a base material and a foamed resin layer provided on the base material,
A foaming agent, a filler, and a resin component containing a silane crosslinkable resin and a polyolefin resin, and when the melt flow rate of all components other than the silane crosslinkable resin in the resin composition is N A resin composition comprising the silane crosslinkable resin, wherein N is 1 to 50 and has a melt flow rate of 0.5 N to 1.5 N.   The manufacturing method of a resin sheet provided with the resin sheet formation process of forming a resin sheet by extrusion-molding the resin composition of Claim 1.   The manufacturing method of a lamination sheet provided with the lamination sheet formation process of laminating the resin sheet obtained by the method of Claim 2 on a base material, and obtaining a lamination sheet.   Cross-linking step of cross-linking part or all of the resin contained in the resin sheet before or during lamination on the substrate, or part of the resin contained in the resin sheet in the laminated sheet Or the manufacturing method of the lamination sheet of Claim 3 further equipped with the bridge | crosslinking process which bridge | crosslinks all.   The manufacturing method of the lamination sheet of Claim 3 or 4 with which the said bridge | crosslinking is performed using superheated steam. A foamed wallpaper manufacturing method comprising: a base material; and a foamed resin layer provided on the base material,
A method for producing foam wallpaper, comprising a foaming step in which a foamed resin layer is formed by foaming the foaming agent contained in the laminated sheet obtained by the method according to any one of claims 3 to 5.