CN113453889B

CN113453889B - Modified film

Info

Publication number: CN113453889B
Application number: CN202080014270.1A
Authority: CN
Inventors: 鱼住京生
Original assignee: Bando Chemical Industries Ltd
Current assignee: Bando Chemical Industries Ltd
Priority date: 2019-02-28
Filing date: 2020-02-27
Publication date: 2024-01-09
Anticipated expiration: 2040-02-27
Also published as: CN113453889A; JP6884271B2; JPWO2020175628A1; WO2020175628A1

Abstract

The invention provides a modified film which combines extinction and hand feeling. The modified film of the present invention is a modified film having a base film, a thermoplastic resin layer, and a top coat layer in this order, the top coat layer containing silica particles and resin beads in a urethane resin, the resin beads containing at least one of acrylic beads and urethane beads.

Description

Modified film

Technical Field

The present invention relates to a modified film.

Background

The decorative film is a resin film that is adhered to the surface of the base material for the purpose of imparting design. As a document disclosing a prior art related to a modified film, patent documents 1 to 5 are cited, for example.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication No. 2017-65261

Patent document 2: japanese patent No. 6413188 specification

Patent document 3: japanese patent laid-open publication No. 2010-234813

Patent document 4: japanese patent laid-open publication No. 2014-69445

Patent document 5: japanese patent laid-open publication No. 2018-199240

Disclosure of Invention

Problems to be solved by the invention

As a decorative film excellent in decorative properties, a decorative film capable of expressing a material other than a resin is required. In order to realize such a modified film, it is required to exhibit high gloss and reproduce the feel of raw materials other than resins.

The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a modified film having both gloss and touch.

Technical means for solving the problems

The modified film of the present invention is a modified film having a base film, a thermoplastic resin layer, and a top coat layer in this order, the top coat layer containing silica particles and resin beads in a urethane resin, the resin beads containing at least one of acrylic beads and urethane beads.

The average particle diameter of the resin beads is preferably 5 μm to 50. Mu.m.

The content of the resin beads is preferably 10 to 30 parts by weight relative to 100 parts by weight of the resin solid content of the top coat layer.

The silica particles preferably have an average particle diameter of 0.1 μm to 10. Mu.m.

The content of the silica particles is preferably 2.5 parts by weight to 30 parts by weight relative to 100 parts by weight of the resin solid content of the top coat layer.

The urethane resin is preferably a silicone copolymerized type polyurethane resin.

Preferably, a print layer is further provided between the base film and the thermoplastic resin layer.

Preferably, the base film further has an adhesive layer on the opposite side of the base film to the side adjacent to the thermoplastic resin layer.

The finishing film is preferably embossed on the top coat side surface.

ADVANTAGEOUS EFFECTS OF INVENTION

The modified film of the present invention can achieve both gloss reduction and touch.

Drawings

Fig. 1 is a cross-sectional view schematically showing an example of the modified film of the present invention.

Description of symbols

1: top coat

2: thermoplastic resin layer

3: printing layer

4: base film

5: adhesive layer

10: modified film

Detailed Description

The modified film of the present invention is a modified film having a base film, a thermoplastic resin layer, and a top coat layer in this order, and is characterized in that the top coat layer contains silica particles and resin beads in a urethane resin, the resin beads containing at least one of acrylic beads and urethane beads. In the present specification, "film" and "sheet" are the same meaning, and they are not distinguished by thickness. In addition, a print layer (ink layer), an undercoat layer (adhesive layer), and the like may be disposed between the base film and the thermoplastic resin layer, and between the thermoplastic resin layer and the topcoat layer.

Fig. 1 is a cross-sectional view schematically showing an example of the modified film of the present invention. The finishing film 10 shown in fig. 1 has a structure in which a top coat layer 1, a thermoplastic resin layer 2, a print layer 3, a base film 4, and an adhesive layer 5 are laminated in this order. The decorative film 10 can be adhered to the substrate by adhering the adhesive layer 5 to the substrate. As a result, the substrate is covered with the finishing film 10, and the top coat layer 1 forms a surface that contacts the space.

[ Top coat ]

The top coat layer 1 is located on the outermost surface of the finishing film 10, and contains silica particles and resin beads in a urethane resin. The matting property can be imparted by the inclusion of silica particles, and the rough texture can be imparted by the inclusion of resin beads. Further, the abrasion resistance (abrasion resistance) is provided by using the urethane resin, and the abrasion resistance can be further improved by adding silica particles to increase the hardness of the top coat layer 1. In particular, by imparting gloss and feel to the topcoat layer 1 according to the pattern of the print layer 3, the decorative properties of the finishing film 10 can be greatly improved. Examples of the pattern of the printed layer 3 for improving the decorative properties of the decorative film 10 include a design for reproducing the surface state of a material other than a resin such as wood, a soil wall, or concrete. It has been difficult to achieve both gloss reduction and durability, but according to the top coat layer 1 having the above-described structure, both gloss reduction and durability can be achieved, and therefore, change in gloss during molding and deterioration in gloss reduction during application (adhesion to a substrate) of the finishing film 10 can be prevented.

The urethane resin is not particularly limited, but is preferably a thermoplastic urethane resin, and particularly preferably a silicone-copolymerized polyurethane resin. If a thermoplastic urethane resin is used, the top coat layer 1 can be embossed after formation, and thus the modified film 10 of various designs can be produced. In addition, by using a silicone copolyurethane resin, both of particularly excellent stain resistance (fingerprint adhesion resistance) and scratch resistance can be provided. In addition, although the film of silicone-copolymerized polyurethane resin gives a smooth feel, by incorporating acrylic beads and urethane beads in the top coat layer 1, a desired rough feel can be imparted.

The silica particles are not particularly limited as long as they are particles containing silica, and the shape and average particle diameter thereof are not particularly limited. The average particle diameter of the silica particles is preferably 0.1 μm or more, more preferably 0.8 μm or more, from the viewpoint of imparting matting properties. If the amount of the additive is the same, the smaller average particle diameter can impart high gloss. In addition, from the viewpoint of preventing the deterioration of the transparency of the top coat layer 1, the average particle diameter of the silica particles is preferably 10 μm or less, more preferably less than 7 μm, and still more preferably 2 μm or less. If the transparency of the top coat layer 1 is too low, visibility of the pattern provided by the print layer 3 is reduced, and the design of the finishing film 10 is impaired. In addition, in the decorative film 10 not provided with the printed layer 3, the visibility of the colored thermoplastic resin layer 2 is lowered, and the design of the decorative film 10 is impaired. As the silica particles, commercially available products such as "Siqigas Series" manufactured by Sakai chemical industry Co., ltd., and "Mizukasil" manufactured by Mizukasil chemical industry Co., ltd., can be used.

From the viewpoint of imparting gloss, the content of silica particles in the top coat layer 1 is preferably 1 part by weight or more, more preferably 2.5 parts by weight or more, and still more preferably 10 parts by weight or more, based on 100 parts by weight of the resin solid content. In addition, from the viewpoint of preventing the decrease in transparency or the excessive increase in haze of the top coat layer 1, the content of silica particles is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, relative to 100 parts by weight of the resin solid content.

The resin beads contain at least one of acrylic beads and urethane beads. The acrylic beads are not particularly limited in shape and average particle diameter as long as they are particles containing an acrylic resin component. The urethane beads are not particularly limited in shape and average particle diameter as long as they are particles containing a urethane resin component. From the acrylic beads and the urethane beads, the feel, for example, of wood, clay wall, or concrete can be reproduced. Further, as a method for imparting a feel, an inorganic bead containing an inorganic material such as glass beads is also considered, but since the acrylic bead and the urethane bead are excellent in adhesion and compatibility with the urethane resin as a main material of the top coat layer 1 and have a specific gravity close to each other, there is an advantage that the falling off from the top coat layer 1 and the sedimentation to the lower portion of the top coat layer 1 are less likely to occur than the inorganic bead. As the acrylic beads, commercially available products such as "chemipno (registered trademark)" manufactured by comprehensive chemical company, "Ai Tepi mol (Art Pearl)" manufactured by root industrial company, and "Gan Zepa lu (ganzpearl)" manufactured by Aica industrial company can be used.

The average particle diameter of the resin beads is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more, from the viewpoint of imparting a feel. In addition, the average particle diameter of the resin beads is preferably 50 μm or less, more preferably 30 μm or less, from the viewpoints of processability and prevention of falling off from the top coat layer 1. Further, the obtained feel can be adjusted according to the particle diameter of the resin beads, and if small beads (10 μm or less) are used, a sandy feel and a fine particle feel are generated, so that a feel like concrete can be obtained. When large beads (10 μm to 30 μm) are used, a feeling of roughness can be imparted, and thus a feeling like a soil wall or wood chips can be obtained. If larger beads (30 μm or more) are used, a hand feel similar to that of coarsely and coarsely shaved wood can be obtained.

From the viewpoint of imparting a feel, the content of the resin beads in the top coat layer 1 is preferably 10 parts by weight or more per 100 parts by weight of the resin solid content. If the amount is less than 10 parts by weight, a sufficient amount of resin beads may not be distributed on the surface of the top coat layer 1, and thus a foreign body sensation may occur. The irregularities on the surface of the top coat layer 1 can be clearly perceived in the range of 10 to 20 parts by weight. In the range of 20 to 30 parts by weight, the resin beads are closely distributed on the surface of the top coat layer 1, thus forming a feeling in which a feeling of roughness is suppressed. The content of the resin beads is preferably 30 parts by weight or less based on 100 parts by weight of the resin solid content. If the amount exceeds 30 parts by weight, the frequency of overlapping of the resin beads increases, and there is a possibility that the resin beads falling off from the surface of the top coat layer 1 increases.

The thickness of the top coat layer 1 is not particularly limited, but is preferably 1 μm to 10 μm.

In order to further improve the design of the print layer 3, the top coat layer 1 is preferably high in transparency, and specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. In the present specification, the total light transmittance is a value based on japanese industrial standard (Japanese Industrial Standards, JIS) K7375.

The top coat 1 may be formed, for example, by applying a top coat forming composition. Examples of the composition for forming a top coat layer include a composition containing a urethane resin, silica particles, resin beads, a solvent, an additive, and the like. As the additive, an ultraviolet absorber, a stabilizer, or the like can be used.

[ thermoplastic resin layer ]

The type of thermoplastic resin used for the thermoplastic resin layer 2 is not particularly limited, and vinyl chloride resin and polyethylene terephthalate (polyethylene terephthalate, PET) resin may be cited, and among them, vinyl chloride resin is preferably used. That is, the thermoplastic resin layer 2 may be a layer generally called a polyvinyl chloride (Polyvinyl chloride) film (PVC film). The thermoplastic resin layer 2 preferably has a function of protecting the surface of the printed layer 3 and has high transparency.

Examples of the vinyl chloride resin include homopolymers of vinyl chloride and copolymers of vinyl chloride with other monomers.

Examples of the other monomers include: vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and styrene; (meth) acrylic esters such as methyl acrylate, ethyl acrylate, and methyl methacrylate; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; cyanoethylene such as acrylonitrile and methacrylonitrile; vinyl halides such as vinylidene chloride and vinyl bromide; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These monomers may be used alone or in combination of two or more.

The content of the other monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. If the amount exceeds 50% by weight, the bending resistance may be lowered. Among the vinyl chloride resins, homopolymers of vinyl chloride are preferable in terms of obtaining dimensional stability.

The average polymerization degree of the vinyl chloride resin is not particularly limited, and may be adjusted according to the required film hardness or the amount of plasticizer used for adjusting the hardness, for example, 750 to 1300. The preferred upper limit of the average polymerization degree is 1050. When the average polymerization degree is in the range of 750 to 1300, the moldability at a relatively low temperature is particularly good. In the present specification, the average polymerization degree of the vinyl chloride resin means an average polymerization degree measured in accordance with JIS K6721 "vinyl chloride resin test method".

The thermoplastic resin layer 2 may also contain a plasticizer. The plasticizer is not particularly limited, and a plasticizer which has been formulated into a vinyl chloride resin from the past can be used, and examples thereof include: diesters of phthalic acid such as octyl phthalate (di-2-ethylhexyl phthalate (Dioctyl Phthalate, DOP)), dibutyl phthalate, dinonyl phthalate, diisononyl phthalate (Diisononyl Phthalate, DINP); aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; triesters of phosphoric acid such as tricresyl phosphate and trioctyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy resin; and high molecular polyester plasticizers.

Examples of the polymer polyester plasticizer include: polyalkylene glycol diesters such as polyethylene glycol diester, polypropylene glycol diester and polyethylene glycol polypropylene glycol diester of phthalic acid; polyethylene glycol diesters of aliphatic dibasic acids such as adipic acid and sebacic acid, polypropylene glycol diesters, and polyalkylene glycol diesters such as polyethylene glycol polypropylene glycol diesters. These plasticizers may be used alone or in combination of two or more. The number average molecular weight of the plasticizer is, for example, 350 to 3000.

The plasticizer is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content is less than 10 parts by weight, the thermoplastic resin layer 2 becomes too hard, and thus the formability is lowered, and there is a possibility that the film may be broken during forming. On the other hand, if it exceeds 30 parts by weight, the thermoplastic resin layer 2 becomes too soft, and the strength thereof decreases, so that it is likely to be easily peeled off from the base material after being adhered thereto. The more preferable lower limit of the content of the plasticizer is 15 parts by weight.

The thermoplastic resin layer 2 may contain additives such as stabilizers, ultraviolet absorbing materials, colorants, foaming agents, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents, if necessary. As these additives, additives generally formulated in thermoplastic resins can be used.

Examples of the stabilizer include: metal soaps such as fatty acid calcium, fatty acid zinc, and fatty acid barium; hydrotalcite, and the like. Examples of the fatty acid component of the metal soap include: calcium laurate, calcium stearate, calcium ricinoleate, zinc laurate, zinc ricinoleate, zinc stearate, barium laurate, barium stearate, barium ricinoleate, and the like. Further, as the stabilizer, an epoxy stabilizer may be used; a barium stabilizer; a calcium stabilizer; a tin stabilizer; a zinc stabilizer; composite stabilizers such as calcium-zinc (Ca-Zn) and barium-zinc (Ba-Zn).

In the case of containing the stabilizer, the content thereof is preferably 0.3 to 5.0 parts by weight relative to 100 parts by weight of the thermoplastic resin. In the case of containing the ultraviolet absorbing material, the content thereof is preferably 0.3 to 2.0 parts by weight based on 100 parts by weight of the thermoplastic resin.

The thickness of the thermoplastic resin layer 2 is not particularly limited, but is preferably 40 μm to 200 μm. If the thickness is less than 40. Mu.m, there is a possibility that the design property may be lowered. On the other hand, if the thickness exceeds 200 μm, there is a possibility that the total heat generation amount of the modified film 10 increases. The more preferable lower limit of the thickness of the thermoplastic resin layer 2 is 50 μm, and the more preferable upper limit is 150 μm.

In order to further improve the design of the printed layer 3, the thermoplastic resin layer 2 is preferably highly transparent, and specifically, the total light transmittance is preferably 80% or more, more preferably 90% or more.

[ printing layer ]

The printing layer 3 is a decorative layer containing a dye or pigment. By disposing the print layer 3, the design of the finishing film 10 can be improved. The printing layer 3 may be a colored film in which a dye or pigment is added to the resin composition, or may be a printing layer in which characters, graphics, or the like are printed on at least a part of the surface of a film containing the resin composition. The dye or the pigment is not particularly limited, and a dye or a pigment generally used in the field of a modified film can be used.

Examples of the resin composition used for the printing layer 3 include: vinyl esters such as vinyl chloride, vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and styrene; (meth) acrylic esters such as methyl acrylate, ethyl acrylate, and methyl methacrylate; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; cyanoethylene such as acrylonitrile and methacrylonitrile; vinyl halides such as vinylidene chloride and vinyl bromide; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These resin compositions may be used alone or in combination of two or more. These resin compositions may be homopolymers or two or more kinds of copolymers.

[ basilemma ]

The base film 4 serves as a support for the finishing film 10 and also serves as a base material for the printing layer 3.

The material of the base film 4 is not particularly limited, and examples thereof include vinyl chloride resin and polyethylene terephthalate resin, and among them, vinyl chloride resin is preferably contained. Since the vinyl chloride resin has high flame retardancy, the use of the vinyl chloride resin as a support for the modified film 10 can suppress an increase in the total heat generation amount. The vinyl chloride resin in the base film 4 may be the same as or different from the vinyl chloride resin used in the thermoplastic resin layer 2 in terms of composition, average molecular weight, and the like.

The base film 4 may also contain a plasticizer. The plasticizer used in the base film 4 may be the same as or different from the plasticizer used in the thermoplastic resin layer 2 in terms of composition, number average molecular weight, and the like.

The plasticizer used in the base film 4 is preferably contained in an amount of 10 to 30 parts by weight relative to 100 parts by weight of the vinyl chloride resin. If the content is less than 10 parts by weight, the base film 4 becomes too hard, whereby the film may be broken at the time of molding. On the other hand, if it exceeds 30 parts by weight, the base film 4 becomes too soft, and thus it may be difficult to form the printed layer 3 on the base film 4. The more preferable lower limit of the content of the plasticizer is 15 parts by weight. Further, since the thermoplastic resin layer 2 and the base film 4 are laminated, it is preferable that the hardness is substantially the same. Therefore, if the thermoplastic resin layer 2 and the base film 4 both contain a vinyl chloride resin and have the same thickness, it is preferable that the plasticizer content is also the same.

The base film 4 may contain additives such as stabilizers, ultraviolet absorbing materials, colorants, foaming agents, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents, if necessary. These additives may be the same as or different from those in the thermoplastic resin layer 2. Further, since the base film 4 is disposed below the ink layer 3, even if an additive is added to the base film 4, it is difficult to visually recognize the change in color tone of the decorative film 10 caused by the additive. Therefore, the base film 4 is suitably added with an additive for adjusting the characteristics of the whole of the modified film 10, and for example, a flame retardant may be formulated.

The thickness of the base film 4 is not particularly limited, and is preferably 40 μm to 200 μm. If the thickness is less than 40 μm, the finishing film 10 may become too soft, and workability may be lowered, or weather resistance may be lowered. On the other hand, if the thickness exceeds 200 μm, there is a possibility that the total heat generation amount of the modified film 10 increases. The more preferable lower limit of the thickness of the base film 4 is 60 μm, and the more preferable upper limit is 150 μm.

In order to improve the adhesion to the printed layer 3, a surface treatment may be performed on the surface of the base film 4. Examples of the surface treatment include corona discharge treatment, plasma treatment, and ozone treatment.

[ adhesive layer ]

The adhesive layer 5 contains an adhesive. Examples of the adhesive include an acrylic adhesive, a rubber adhesive, and a silicone adhesive. Among them, acrylic adhesives are preferably used in terms of excellent adhesion, processability, heat aging resistance, humidity aging resistance, weather resistance and relatively low cost.

The acrylic adhesive is an adhesive containing an acrylic polymer. Examples of the acrylic polymer include homopolymers of alkyl (meth) acrylates and copolymers thereof.

The adhesive layer 5 can be formed, for example, by a method of applying an adhesive composition containing an adhesive, a crosslinking agent (hardening agent), or the like to a support to form a coating film, and then drying the coating film by heating to harden the coating film. The crosslinking agent (hardener) is a compound that chemically reacts or interacts with the functional groups in the adhesive and crosslinks it. As the crosslinking agent, known crosslinking agents such as isocyanate-based curing agents and epoxy-based curing agents can be used.

The adhesive composition may contain various additives such as stabilizers, plasticizers, softeners, fillers, adhesion imparting agents, dyes, pigments, and inorganic fillers, if necessary.

The adhesive composition is preferably applied in an amount of 5g/m ² ～90g/m ² (weight conversion during drying). In other words, it is preferable that the coating amount of the adhesive layer 5 after drying the adhesive composition is 5g/m ² ～90g/m ² . A more preferable lower limit of the coating amount is 10g/m ² . A more preferable upper limit of the coating amount is 60g +.m ² 。

The thickness of the adhesive layer 5 is preferably 10 μm to 60 μm. If the thickness is less than 10. Mu.m, sufficient tackiness may not be obtained. On the other hand, if the thickness exceeds 60 μm, there is a possibility that the total heat generation amount of the modified film 10 increases. The more preferable lower limit of the thickness of the adhesive layer 5 is 20 μm, and the more preferable upper limit is 50 μm. The thickness of the adhesive layer 5 is the thickness after drying.

[ spacer ]

The finishing film 10 may be provided with a spacer on the side of the adhesive layer 5 opposite to the base film 4. By providing the spacers, the adhesive layer 5 is not exposed during the production, transportation, and storage of the dressing film 10, and thus deterioration of the adhesive layer 5 can be prevented and the operability of the dressing film 10 can be improved. The spacer may be peeled off just before being attached to the substrate.

The spacer is not particularly limited, and a spacer generally used in the field of a modified film can be used. The spacer is preferably a spacer that can be easily peeled off without damaging the adhesive layer 5, and examples thereof include a resin film (release film), paper (release paper), and a laminated film of paper and a coating layer. The release film may be: and resin films such as polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene. The resin film is preferably subjected to an easy-release treatment by coating a silicone resin, a fluororesin, or the like on the surface in contact with the adhesive layer 5. Examples of the release paper include high-quality paper and cellophane.

The finishing film 10 may be subjected to surface processing such as embossing processing on the surface of the top coat layer 1 side as needed. When an embossed shape (concave-convex shape) is imparted to the surface of the finishing film 10 by embossing, the visual and tactile texture can be further improved. The embossing process may be performed on the surface of the top coat layer 1, or may be performed on the surface of the thermoplastic resin layer 2 before the top coat layer 1 is formed. In the case where the top coat layer 1 includes a thermoplastic urethane resin, embossing processing may be performed after the formation of the top coat layer 1, and thus the finishing film 10 of various designs may be manufactured.

The total thickness of the organic resin layer of the finishing film 10 is preferably 100 μm to 500 μm. If the total thickness is less than 100. Mu.m, workability may be lowered or weather resistance may be lowered. On the other hand, if the total thickness exceeds 500 μm, it may be difficult to suppress the total heat generation amount. The total thickness of the organic resin layer means the sum of the thicknesses of the top coat layer 1, the thermoplastic resin layer 2, the print layer 3, the base film 4, and the adhesive layer 5. The total thickness of the organic resin layer does not include the thickness of the spacer. The more preferable lower limit of the total thickness of the organic resin layer is 120 μm, and the more preferable upper limit is 300 μm.

The total heat generation amount of the modified film 10 is preferably 7.2MJ/m ² The following is given. The total heat generation amount is the total heat generation amount in the heat generation property test by a cone calorimeter (cone calorimeter) tester according to the fire prevention test method of the item 2 and the performance evaluation standard of the item 108 based on the construction reference method, item 9 and the construction reference method. The measurement of the total heat quantity is performed according to a heat generation test method of fire resistance test/evaluation service method book of (financial) building material test center. Specifically, a gypsum board having a thickness of 12mm or more was used as a base material, and a heat-generating property test apparatus (cone calorimeter) for a fireproof material was used. The gypsum board is laminated with base paper/gypsum/base paper in sequence, and the heating value is highest in the nonflammable materials. Therefore, if the heat generating test using gypsum board is suitable, other nonflammable materials can be considered as suitable for the heat generating test. If the total heating value 20 minutes after the start of heating is 7.2MJ/m ² Hereinafter, the reference of the total heat generation amount (8 MJ/m ² The following are described below). The modified film 10 of the present invention preferably satisfies the requirements of "no cracks or holes penetrating to the back surface, which are harmful in terms of fire prevention, 20 minutes after the start of heating" and "the maximum heat generation rate of 20 minutes after the start of heating lasts 10 seconds or more and does not exceed 200 kW/m" described in the "fire resistance test/evaluation service method Specification ² "reference.

The modified film 10 can be manufactured by a known manufacturing method. The top coat layer 1 may be formed by, for example, a conventionally known method such as a method of applying a top coat layer-forming composition onto the thermoplastic resin layer 2 by a bar coating method, a roll coating method, a doctor blade coating method, a reverse coating method, a gravure coating method, a die coating method, or the like, and then curing the coating film by heat drying, ultraviolet irradiation, or the like.

The thermoplastic resin layer 2 and the base film 4 can be produced by a conventionally known molding method such as calender molding, extrusion molding, injection molding, or the like. Examples of the rolling form used in the rolling formation include an inverted L-shape, a Z-shape, an upright 2-root shape, an L-shape, and an inclined 3-root shape.

The printing layer 3 may be formed by a conventionally known printing method such as inkjet printing or gravure printing.

The method for forming the adhesive layer 5 is not particularly limited, and a conventionally known method such as a method of directly applying the adhesive composition to the spacer by a bar coater or the like and drying the same can be used. In this case, the finishing film 10 can be manufactured by attaching the adhesive layer 5 formed on the spacer to the base film 4. The finishing film 10 is further subjected to a process such as cutting and winding into a roll shape as needed.

In the case of embossing the modified film 10, the following may be applied, for example.

The laminate in which the top coat layer 1, the thermoplastic resin layer (vinyl chloride resin layer) 2, the print layer 3 and the base film 4 are laminated in this order is heated by a preheating roller, and after softening the top coat layer 1 and the thermoplastic resin layer 2, the laminate is peeled off from the preheating roller and nipped by an embossing roller and a rubber roller to form irregularities. The pressure during clamping is set to 20kg/cm ² . By the method, for example, in the case of adding 17 parts by weight of acrylic beads having an average particle diameter of 30 μm to 100 parts by weight of the resin solid content in the top coat layer, ra: 6-7 μm, rz: 23-26 μm, ry: a surface roughness of about 24 μm to 35 μm (JIS 1994) gives a feeling of roughness stronger than that of the case where embossing is not performed.

The application of the finishing film of the present invention is not particularly limited, and examples thereof include finishing sheets (wall finishing materials) attached to a wall surface, interior finishing materials such as interior doors, closet doors or kitchen doors, furniture, floors, and the like. In addition, the wall decoration can also be used for wall decoration of water-using places such as bathrooms, kitchen rooms, toilets and the like. According to the modified film of the present invention, the same design as a coated article can be obtained by a simpler and safer method than coating.

Examples

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1

27 parts by weight of diisononyl phthalate (DINP) was added as a plasticizer to 100 parts by weight of polyvinyl chloride (PVC) having an average polymerization degree of 1000 to obtain a PVC mixture (compound). After the obtained PVC mixture was melt-kneaded by a banbury mixer, the resultant was formed into a sheet having a thickness of 80 μm by an inverted L-shaped calender, and a PVC film was produced. The obtained PVC film was used as a top film (thermoplastic resin layer) and a base film.

Next, a printed layer was formed on one side of the base film using an inkjet printer using a vinyl chloride-vinyl acetate copolymer/acrylic ink. Next, a top film was laminated on the surface of the base film on which the printed layer was formed by thermal lamination, to produce a laminated film.

A top coating composition was obtained by adding 100 parts by weight of a Razid (Razoid) LU-504SP, a nonvolatile component of 18.4.+ -. 1.5%, 1 part by weight of silica particles having an average particle diameter of 0.1. Mu.m (manufactured by Shimadzus Series (Sciqas Series)) and 20 parts by weight of acrylic beads having an average particle diameter of 0.8. Mu.m (manufactured by Heald chemical Co., ltd.) to 100 parts by weight of a urethane surface treatment agent containing a silicone copolymerized polyurethane resin (manufactured by Dairy refining Industrial Co., ltd., product name: kamino (Chemisnow)), and adjusting the viscosity with diluted methyl ethyl ketone. The obtained composition for a top coat was applied on a top film of the laminated film using a bar coater, and dried at 85℃for 2 minutes to form a top coat layer having a thickness of 6. Mu.m. As a result, a laminate in which a top coat layer, a top film (thermoplastic resin layer), a print layer, and a base film were laminated in this order was obtained.

Further, an acrylic adhesive solution was applied to one surface of a spacer (biaxially oriented Polyester (PET) film) having a thickness of 100 μm by a bar coater so as to dry the film to a thickness of 40 μm, thereby forming a coating film. The acrylic adhesive solution was prepared by blending 1.2 parts by weight of an epoxy hardener (E-AXM manufactured by holly-grinding chemistry company) with 100 parts by weight of an acrylic adhesive (SK 2094 manufactured by holly-grinding chemistry company). The adhesive layer was produced by drying the coating film in a drying oven at 80 ℃ for 1 minute to remove the solvent in the coating film.

Next, the spacer and the laminate are bonded via an adhesive layer, and the adhesive layer formed on the spacer is transferred to the base film side of the laminate. Thus, a modified film of example 1 was obtained.

(example 2-example 21 and comparative example 1)

Modified films of examples 2 to 21 and comparative example 1 were produced in the same manner as in example 1, except that silica particles and resin beads added to the top coat layer were changed as shown in table 1 below.

(evaluation test)

The modified films produced in examples and comparative examples were evaluated by the following methods. The results are shown in table 1 below.

(1) Haze and transmittance

In order to evaluate the influence of the difference in the composition of the top coat layer on the optical characteristics, the top coat layer compositions used in examples and comparative examples were applied to a PET substrate (manufactured by Unitika) manufactured by the company You Niji under the product name S-25 to prepare test specimens having a top coat layer provided on the PET substrate. The haze and transmittance of the measurement sample were measured using a haze meter "haze meter (HazeMeter) NDH5000" manufactured by japan electric color industry company. Haze was measured by the method according to "JIS K7136". The transmittance was measured by the method according to JIS K7361-1.

(2) Transparency of

The modified film was visually observed from the top coat side and evaluated according to the following criteria.

O: the reduction in appearance relative to the design of the printed layer is small

Delta: there is a possibility that the appearance with respect to the design of the printed layer may be degraded

X: confirming the decrease in appearance relative to the design of the printed layer

(3) Extinction of light

And (3) the following materials: has high extinction property

O: has extinction property

X: no extinction property

(4) Hand feel

The surface of the top coat layer of the finishing film was touched by hand and evaluated according to the following criteria.

O: unlike the usual resin film, a high texture like wood, soil wall or concrete is obtained

Delta: imparting a feel different from that of a usual resin film

X: the hand feeling is not greatly different from that of the common resin film

In Table 1, the unit "phr" of the addition amount of the resin beads and the silica particles represents parts by weight relative to 100 parts by weight of the resin solid content in the top coat layer.

From the results shown in Table 1, it was found that the silica particles had an average particle diameter of 0.1 μm to 10. Mu.m, and that the silica particles had a high extinction property of 0.8 μm to 10. Mu.m. Further, it is known that the addition amount of silica particles is large to improve the extinction, but if it is too large, the haze is increased or the transparency is lowered. Further, the average particle diameter of the resin beads is in the range of 5 μm to 50. Mu.m, and the feel can be obtained.

Claims

1. A finishing film comprising a base film, a thermoplastic resin layer and a top coat layer in this order,

the finishing film is embossed on the surface of the top coating side, and

the top coat layer contains silica particles and resin beads in a thermoplastic silicone copolyurethane resin,

the resin beads contain at least one of acrylic beads and urethane beads,

the resin beads have an average particle diameter of 10 μm or more,

the content of the resin beads is 10 to 30 parts by weight based on 100 parts by weight of the resin solid content of the top coat layer.

2. The modified membrane of claim 1, wherein the resin beads have an average particle diameter of 10 μm to 50 μm.

3. The modified film according to claim 1 or 2, wherein the silica particles have an average particle diameter of 0.1 μm to 10 μm.

4. The modified film according to claim 1 or 2, wherein the silica particles are contained in an amount of 2.5 to 30 parts by weight based on 100 parts by weight of the resin solid content of the top coat layer.

5. The modified film according to claim 1 or 2, further comprising a printed layer between the base film and the thermoplastic resin layer.

6. The modified film according to claim 1 or 2, further comprising an adhesive layer on the opposite side of the base film to the side adjacent to the thermoplastic resin layer.