JP2015217620A - Base film for polyolefin resin cosmetic sheets, cosmetic sheet and building interior decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base film for polyolefin resin cosmetic sheets that has excellent film forming properties, and offers a decorative sheet with a good appearance regardless of the quality of a surface of substrate material or the like.SOLUTION: The base film for polyolefin resin cosmetic sheets is a base film used for polyolefin resin cosmetic sheets, having a thickness of 145 μm-300 μm and a yield value of 40-100 N/cm.

Description

  The present invention relates to a polyolefin resin-based substrate film. In particular, the present invention is a polyolefin resin-based makeup that is excellent in film forming and concealing properties and has a good appearance when applied to a wooden substrate without being affected by the surface quality of the wooden substrate (underlying material). The present invention relates to a base film for providing a sheet, a decorative sheet using the same, and a decorative material for architectural interior.

  Cosmetic materials such as decorative plywood used for furniture and architectural interior materials are well known in that printed decorative sheets are pasted on base materials such as wood and steel plates such as plywood. As a material for the decorative sheet, paper and plastic film are widely used.

  As a material for a plastic film for a decorative sheet, conventionally, a vinyl chloride resin excellent in design and adhesiveness has been used. However, in recent years, decorative sheets based on polyolefin resins have been demanded due to problems such as treatment of hydrogen chloride gas generated during incineration disposal after use and selection of furnace materials for incinerators used therefor. I came. Among them, a decorative sheet based on a polypropylene resin film is often used as a film for a decorative sheet because it has a good balance between rigidity and flexibility.

  At present, a decorative sheet based on this polyolefin-based resin is generally used in a thickness of about 0.2 to 0.5 mm as a commonly used thickness. A base layer, a transparent layer, a concealing layer, printing A technique for imparting performance required as a decorative sheet by having a multilayered layer structure such as a layer, an adhesive layer, and a protective layer is used.

  For example, Japanese Patent Laid-Open No. 10-67081 (Patent Document 1) discloses a decorative sheet containing a polyolefin resin film as a constituent layer, and includes a base film layer, a printing layer, a transparent coating film layer, wiping coating, and surface protection. A decorative sheet is disclosed that is composed of layers and has a base film thickness of 100 μm.

  Japanese Patent Application Laid-Open No. 2009-292079 (Patent Document 2) discloses a makeup made of a polypropylene resin base sheet having a pattern ink layer having a thickness of 70 μm, an adhesive layer, a transparent polyolefin resin layer, and a surface protective layer. A sheet is disclosed.

  Thus, various technologies for polyolefin resin-based decorative sheets have been used in the past, but the base film used in this polyolefin resin-based decorative sheet has not been thick, and is usually 100 μm. The following are used.

Japanese Patent Laid-Open No. 10-67081 JP 2009-292079 A

The material used for the base material such as plywood and steel plate of the prior art, because the surface of the material, etc., has been used many quality materials, so when using a decorative sheet with a thickness as in the prior art Was able to be made into a cosmetic material with excellent appearance.
However, in recent years, the price of materials has increased and the use of overseas base materials has increased, and the use of low quality materials such as the surface of base materials has increased.

  In order to use a base material having a low surface quality for a decorative sheet, it is possible to hide the surface of the base material to some extent by increasing the thickness of the decorative sheet. However, if the thickness of the decorative sheet is increased, the rigidity of the decorative sheet increases, and the film-forming property deteriorates in the process of producing the decorative sheet. In addition, there are problems such as poor handling of secondary processing.

An object of the present invention is to provide a base film for a polyolefin resin-based decorative sheet that has good film forming properties and good appearance of a decorative board regardless of the quality of the surface of the base material and the like.
Another object of the present invention is to impart high designability to a decorative board formed by bonding the decorative sheet to a substrate by imparting rigidity and high concealment suitable for the base film.

  As a result of intensive studies, the present inventors have found that the base film used in the polyolefin resin-based decorative sheet has a thickness of 145 to 300 μm, a yield value of 40 to 100 N / cm, and can also provide high concealment. The inventors have completed the invention of a base film for a polyolefin resin-based decorative sheet that has excellent designability when bonded to a substrate.

That is, the present invention
[1] A base film for a polyolefin resin-based decorative sheet, which is used for a polyolefin resin-based decorative sheet and has a thickness of 145 μm to 300 μm and a yield value of 40 to 100 N / cm.
[2] In the concealment rate test paper defined in JISK5600, the color difference between the case where the base film is laid on a white member and the case where it is laid on a black member is 2.0 or less. The base film for polyolefin resin-based decorative sheets according to 1].
[3] The base film for a polyolefin resin-based decorative sheet according to [1] or [2], wherein the base film contains at least a polypropylene resin.
[4] The polyolefin resin-based base sheet for decorative sheet according to [3], wherein the polypropylene-based resin contains a homopolymer of propylene.
[5] At least a surface layer, an intermediate layer, and a back layer,
The thickness of the intermediate layer is 50% to 99.9% with respect to the thickness of the entire film,
The polyolefin resin system according to any one of [1] to [4], wherein the content of the pigment contained in the intermediate layer is greater than the content of the pigment contained in the surface layer and the back layer. Base film for decorative sheet.
[6] A polyolefin resin decorative sheet using the base film for a polyolefin resin decorative sheet according to any one of [1] to [5].
[7] A decorative material for architectural interiors, wherein the base film side surface of the polyolefin resin decorative sheet described in [6] is attached to an adherend.
Is provided.

  According to the present invention, even when a substrate having a large surface roughness or undulation such as a plywood or a rough one is used, the surface does not have an unevenness or undulation, and high concealment and mirror surface properties are required. In addition, a decorative sheet capable of maintaining high quality can be provided, and a base film for a polyolefin resin-based decorative sheet having good film forming properties can be provided.

  It is important that the base film of the present invention has a thickness of 145 μm to 300 μm, preferably 170 μm to 280 μm, and more preferably 190 μm to 260 μm. By setting the thickness of the base film to 145 μm or more, the surface irregularities and undulations of the plywood and the like used for the substrate can be made inconspicuous. Moreover, by making the thickness of the base film to be 300 μm or less, it is possible to obtain a base film having a good appearance and a uniform appearance.

  Moreover, it is important that the base film of the present invention has a yield value of 40 N / cm to 100 N / cm, preferably 45 N / cm to 95 N / cm, and 50 N / cm to 90 N / cm. More preferably. By setting the yield value within the above range, it is possible to impart excellent design properties without affecting the appearance of the decorative board for surface irregularities and undulations such as plywood used for the substrate.

  Furthermore, the base film of the present invention has a color difference of 2.0 or less when the base film is laid on a white member and on a black member in the concealment rate test paper defined in JISK5600. Preferably, it is preferably 1.5 or less, and more preferably 1.0 or less. The color difference between the case where it is laid on a white member and the case where it is laid on a black member is 2.0 or less, so that it is excellent in concealment with respect to surface patterns such as plywood used for the base material. As a layer structure, it is possible to eliminate the necessity of providing another concealing layer or printing layer. Further, the lower limit value of the color difference is not particularly limited, but it is preferable that the color difference is closer to 0 in consideration of high concealment performance.

  The polyolefin resin that can be used for the base film of the present invention may be a polyethylene resin or a polypropylene resin, and preferably contains at least a polypropylene resin.

<Polyethylene resin>
The polyethylene resin used in the present invention is an ethylene homopolymer, a copolymer of ethylene and other monomers copolymerizable with ethylene (low density polyethylene (LDPE), high pressure method low density). Examples include polyethylene, linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene-α-olefin copolymers (metallocene polyethylene, etc.) obtained by polymerization using a metallocene catalyst, and mixtures thereof. it can.

<Polypropylene resin>
Examples of the polypropylene-based resin used in the present invention include a propylene homopolymer, a copolymer, or a mixture (polymer blend) of the homopolymer and / or the copolymer with another polymer. Examples of the copolymer include a random copolymer or block copolymer of propylene and ethylene or another α-olefin, or a propylene graft copolymer using a polyolefin-based copolymer as a backbone polymer. .

  Moreover, it is preferable that the polypropylene resin used for this invention contains the homopolymer of propylene, and the ratio of the homopolymer of propylene is 50 mass parts or more with respect to the total mass of a base film. Is more preferable, and 55 parts by mass or more is even more preferable. By including a propylene homopolymer, it becomes possible to give the film an appropriate rigidity. Further, the upper limit of the content of the propylene homopolymer is not particularly limited, but it is preferably 90 parts by mass or less from the viewpoint that flexibility is not deteriorated and handling property is improved. Furthermore, since the glass transition temperature of the film can be lowered by adding random PP, it is preferable because it is difficult to become brittle at low temperatures and the physical properties are improved.

<Nucleating agent>
In addition, a nucleating agent can be added to the polyolefin resin used in the present invention in order to give the film rigidity. As the nucleating agent, a commercially available nucleating agent can be used, for example, metal salts of benzoic acids such as sodium benzoate, aluminum-p-tert-butylbenzoate, lithium-p-tert-butylbenzoate; 2 , 2-methylenebis (4,6-ditertiarybutylphenyl) phosphate ester metal salts such as sodium phosphate; dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, bis (4-ethylbenzylidene) sorbitol, etc. Benzylidene sorbitols; metal alcoholates such as glycerin zinc; amino acid metal salts such as zinc glutamate; aliphatic dibasic acids having a bicyclo structure such as bicycloheptanedicarboxylic acid or salts thereof; and metal salts thereof, sodium benzenesulfonate, p- Toluenesulfone And aromatic sulfonic acid metal salt such as lithium and the like.

  Moreover, it is preferable to set it as 0.015-0.5 mass part per 100 mass parts of polyolefin resin, and, as for the compounding quantity of a nucleating agent, it is more preferable to set it as 0.025-0.4 mass part. By setting the blending amount to 0.015 parts by mass or more, the effect of nucleation of the nucleating agent can be obtained and the rigidity can be improved. Moreover, if it is 0.5 mass part or less, the effect of a nucleating agent is fully acquired, a nucleating agent is not used more than necessary, and material cost can be reduced.

<Inorganic filler>
In addition, an inorganic filler can be added to the base film of the present invention in order to give the film rigidity. Examples of the inorganic filler that can be used for the base film of the present invention include calcium carbonate, talc, mica, barium sulfate, aluminum hydroxide, magnesium hydroxide, and silica.

The base film of the present invention comprises at least a surface layer, an intermediate layer, and a back layer, the ratio of the thickness of the entire base film is 50% to 99.9%, and the content of the pigment in the intermediate layer is the surface layer, It is preferable that the content of the pigment in the back layer is larger than that of the back layer, or it is more preferable that the pigment is contained only in the intermediate layer. In this way, even if the amount of the pigment is increased, the intermediate layer of the film contains a large amount of pigment, and the addition amount of the surface layer and the back layer is reduced or not added as much as possible. It is possible to preferentially prevent the occurrence of scum. Therefore, it is possible to obtain a film with high concealment and good film forming property.
In addition, not adding a pigment includes adding a very small amount that does not affect the performance.

  As the pigment, any of organic pigments and inorganic pigments can be used. Examples thereof include titanium oxide, carbon black, iron oxide, azo compounds, phthalocyanine compounds, titanium oxide / antimony oxide / nickel oxide solid solution, and the like. The pigment content is preferably in the range of 0.5 to 70 parts by mass with respect to 100 parts by mass of the polyolefin-based resin, although it depends on the concealment required for the decorative sheet. More preferably, it is contained in the range of 3 to 50 parts by mass. By including the pigment in the above range, the concealability is improved.

The base film of the present invention preferably contains an ultraviolet absorber and / or a hindered amine light stabilizer.
The blending amount of the ultraviolet absorber is preferably from 0.01 to 10 parts by weight, particularly preferably from 0.05 to 5 parts by weight, per 100 parts by weight of the polyolefin resin in each layer. If the blending amount is 0.01 parts by mass or more, an effect of preventing browning and deterioration is easily obtained, and if it is 10 parts by mass or less, an effect commensurate with the blending amount is obtained and there is no possibility of causing bleeding.

  As an ultraviolet absorber used for the base film of the present invention, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzo Triazole (molecular weight 388), 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (molecular weight 448), 2,2-methylenebis [4- (1,1 , 3,3-tetramethylbutyl-6- (2H-benzotriazol-2-yl) phenol] (molecular weight 659), and 2,4-dihydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzopheno And benzophenone-based ultraviolet absorbers such as bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane.

  Among the ultraviolet absorbers, it is preferable to use a benzotriazole-based ultraviolet absorber in order to reduce the coloring of the product, and the molecular weight thereof is in the range of 380 to 1000, preferably in the range of 400 to 800. Those within are more preferred. By setting the molecular weight within the above range, the bloom preventing effect is further increased.

  The amount of the hindered amine light stabilizer is preferably 0.01 to 10 parts by mass per 100 parts by mass of the polyolefin resin in each layer. If the blending amount is 0.01 parts by mass or more, a stabilizing effect is easily obtained, and if it is 10 parts by mass or less, an effect commensurate with the blending amount is obtained and there is no possibility of causing bloom.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Polycondensates and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl Examples thereof include hindered amine light stabilizers such as -4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}].

  Furthermore, other synthetic resins and additives such as antioxidants, slip agents, colorants, fillers, and nucleating agents are added to the base film of the present invention as long as the purpose of the present invention is not impaired. May be. Moreover, about these additives, it is common to use what was previously mix | blended with resin at high concentration (masterbatch).

  As a method for producing the base film of the present invention, a general polyolefin resin film molding method such as a T-die extrusion molding method, an inflation molding method and a calendar molding method may be used, but the appearance is good. In view of producing a base film having a uniform thickness, it is preferable to use a T-die extrusion method.

<T-die molding method>
The T-die molding method that can be used in the present invention is a nip molding method in which the molten resin extruded from the T-die is sandwiched between two rolls in that a film having a more uniform thickness can be obtained. Is preferred.

As for the material of the two rolls used for the nip molding that can be used in the present invention, it is preferable that at least one of the rolls is a metal roll. By forming at least one roll as a metal roll, even when a thick film is formed, the cooling efficiency of the base film is improved, and the accuracy of the thickness can be further stabilized. The surface roughness can also be suitable.
The material of the other roll can be appropriately set according to the physical properties of the molten resin to be used. For example, the other roll can be a rubber roll, or can be a metal roll or a roll of another material.

  The surface roughness of the roll is preferably 0.05 to 4.0 [mu] m, more preferably 0.1 to 3.0 [mu] m, according to JIS B0601: 2001. Furthermore, the maximum height roughness Rz of the roughness curve is preferably 0.5 to 30 μm, and more preferably 1 to 20 μm. By setting the surface roughness of the roll as described above, a suitable surface shape can be obtained as the base film used for the polyolefin resin-based decorative sheet.

Another aspect of the present invention is a decorative sheet using the above-described base film for a polyolefin-based decorative sheet.
In general, the surface of the decorative sheet is often provided with a surface layer in order to improve the weather resistance, abrasion resistance, scratch resistance, etc. of the decorative material. This layer is a polyolefin resin, polyester resin, acrylic resin, It can be formed by laminating or coating urethane resin or the like. You may emboss this surface layer.

  Moreover, you may provide a printing layer between the surface layer of a decorative sheet, and a base film as needed. The printing layer can be formed by a transfer method in addition to a method of printing by gravure printing, offset printing, offset gravure printing, silk screen printing, or the like using an ink in which pigments are dispersed. . In order to improve the adhesion between the printed layer and the base material sheet for decorative material, it is desirable to perform corona treatment on the surface of the base material sheet for decorative material to be printed. In addition, it is preferable to provide a primer layer between the substrate sheet and the printing layer because the adhesion between the two is further improved. This primer layer can be formed from a solution containing chlorinated polyolefin resin, polyester resin, ethylene-vinyl alcohol copolymer or the like as a main component and, if necessary, added with a filler.

Another aspect of the present invention is a decorative material for architectural interiors, wherein the back surface of the base film of the polyolefin-based decorative sheet is adhered to an adherend.
By using the polyolefin-based decorative sheet having the base film of the present invention in a layer structure, it is excellent in appearance as a decorative material for building interiors even when a material having large surface irregularities or undulations is used. Things can be created.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following examples, unless the summary is exceeded.
<Examples 1-7, Comparative Examples 1-2>
Production of base film for polyolefin resin-based decorative sheet Using the formulation shown in Table 1, using a T-die extruder (T die: 650 mm width) with one 50 mmφ extruder and two 35 mmφ extruders, the die temperature 230 ° C., one of the rolls is a metal roll and the other is a rubber roll. The surface roughness of the roll is an arithmetic average roughness Ra of 0.8 μm according to JIS B0601: 2001, and the maximum height roughness Rz of the roughness curve. The base film for a decorative sheet having a thickness of 140 to 400 μm and a thickness of 140 to 400 μm was prepared.

The following evaluation was performed about the obtained film. The results are shown in Table 1.
[Evaluation method]
1) Tensile elastic modulus The obtained film was heat-treated in a gear oven set at 110 ° C for 60 minutes, then cured at 23 ° C for 24 hours, and the measurement part specified in JIS K 7127 was formed into a 1 cm wide dumbbell shape. A sample was prepared by punching. The obtained sample was measured at a test temperature of 23 ° C., a gap between chucks of 4 cm, and a tensile speed of 50 mm / min. The results are shown in Table 1.

2) Color difference (ΔE)
When the film is placed on the white part of the concealment rate test paper defined by JIS K 5600 and when it is placed on the black part, a light source D-65 and an incident angle of 10 using a SPECTROPHOTOMETER CM-2500d manufactured by KONICA MINOLTA The color measurement was carried out at °, the color difference (ΔE) was calculated, and the results are shown in Table 1.

3) Film forming property The film forming property at the time of manufacturing was evaluated according to the following criteria.
○: Film with good appearance can be stably formed ×: Appearance deteriorates throughout the film

In the table, “homo PP” is FLX80E4 (manufactured by Sumitomo Chemical), “random PP” is FX3B (manufactured by Nippon Polypro), “pigment MB” is 65 wt% titanium oxide, 30 wt% random PP, The other dispersant is 5% by weight.
In addition, the numerical value of the addition amount of the pigment MB in the table is part by mass when the total amount of the resin contained in the intermediate layer is 100 parts by mass.

Claims (7)

  A base film for a polyolefin resin-based decorative sheet, which is used for a polyolefin resin-based decorative sheet and has a thickness of 145 μm to 300 μm and a yield value of 40 to 100 N / cm.   In the concealment rate test paper defined in JISK5600, the color difference between the case where the base film is laid on a white member and the case where the base film is laid on a black member is 2.0 or less. The base film for polyolefin resin-type decorative sheets as described.   The base film for a polyolefin resin-based decorative sheet according to claim 1 or 2, wherein the base film contains at least a polypropylene-based resin.   The said polypropylene resin contains the homopolymer of propylene, The base film for polyolefin resin type decorative sheets of Claim 3 characterized by the above-mentioned. Having at least a surface layer, an intermediate layer, a back layer,
The thickness of the intermediate layer is 50% to 99.9% with respect to the thickness of the entire film,
5. The polyolefin resin decorative sheet according to claim 1, wherein the content of the pigment contained in the intermediate layer is greater than the content of the pigment contained in the front layer and the back layer. Substrate film.   A polyolefin resin-based decorative sheet comprising the base film for a polyolefin resin-based decorative sheet according to any one of claims 1 to 5.   A decorative material for architectural interiors, wherein the base film side surface of the polyolefin resin decorative sheet according to claim 6 is adhered to an adherend.