JP2021030628A - Release film for vehicle decorative pressure sensitive adhesive sheet, laminate film for vehicle decorative pressure sensitive adhesive sheet and vehicle decorative pressure sensitive adhesive sheet - Google Patents

Abstract

To provide a release film excellent in releasability because of being free from wrinkle and unevenness even when used in vehicle decorative application, a laminate film suitable for various kinds of applications including a marking film having excellent high gloss, scratch resistance, surface followability and adhesion workability by using the release film, and a vehicle decorative pressure sensitive sheet using the same.SOLUTION: A release film for vehicle decorative pressure sensitive adhesive sheets, at least one side of which contains a base film showing elongation (i) in the following range when thermomechanically analyzing under the following condition. (Condition) Test piece size: width 4 mm × length 40 mm, distance between chucks: 8 mm, measurement atmosphere: under nitrogen atmosphere (nitrogen flow rate 100 ml/minute), rate of temperature increase : 10°C/minute (initiation temperature: 23°C, finishing temperature: 240°C), load: 400 mN, (elongation (i)) an absolute value of the elongation of the base film at 125°C is 40 μm or smaller.SELECTED DRAWING: None

Description

The present invention provides a release film for a vehicle decorative adhesive sheet used for imparting design to a vehicle such as a bicycle, a motorcycle, or an automobile, a laminated film for a vehicle decorative adhesive sheet, and a vehicle decoration using the same. Regarding adhesive sheets.

Conventionally, decorative adhesive films (tapes) such as stickers, labels and marking films, decorative sheets, etc., which are attached to give design to industrial adhesive films (tapes), signs, automobiles, etc., are colored. Polyvinyl chloride resin films and polyolefin resin films, which are excellent in properties, processability, scratch resistance, weather resistance, etc., have been widely used as raw film.

Adhesive films such as marking films that use polyolefin resin films as the base material are known, and in response to the demand for films with appropriate flexibility, the base material is blended with an elastomer component, and the base material is coated with acrylic-modified urethane. An adhesive film having improved scratch resistance and durability by laminating films is known (Patent Document 1).
In addition, we propose a laminated film suitable for various applications, including a marking film that uses a polyolefin-based resin with excellent flexibility, has high gloss, and has good scratch resistance, curved surface followability, and sticking workability. (Patent Documents 2 and 3)

By using the films described in Patent Documents 1 to 3, it is possible to impart scratch resistance and durability to a molded product having a three-dimensional shape. Further, since it has excellent glossiness, it is possible to obtain a molded product having a beautiful appearance, and it is possible to suitably use it for interior and exterior applications of vehicles such as automobiles.

However, with the increasing demand for beautiful appearance, molded products used for the interior and exterior of vehicles tend to be required to have a film having further improved glossiness and excellent appearance.
In the method using the films described in Patent Documents 2 and 3, sufficient gloss cannot be imparted depending on the type of the released film to be laminated, and wrinkles and irregularities occur in the release film when the release layers are laminated. In some cases, the obtained film or molded product also had a poor appearance or lacked glossiness.
Further, depending on the type of the release layer, there are problems such as insufficient peeling from the release layer and deterioration of the appearance when peeled. Further, there is room for improvement from the viewpoints of wrinkles and irregularities of the release film when the laminated film is wound by the roll-to-roll method, and the appearance of the obtained laminated film.

Japanese Unexamined Patent Publication No. 2004-2825 JP-A-2007-83530 JP-A-2007-297569

The present invention has been made in view of the above problems, and is a release film having excellent releasability without wrinkles or irregularities even when used for a vehicle decorative adhesive sheet, and a high gloss using the releasable film. An object of the present invention is to provide a laminated film for a vehicle decoration adhesive sheet and a vehicle decoration adhesive sheet suitable for various applications such as a marking film having good scratch resistance, curved surface followability, sticking workability, etc. And.

The present inventors have diligently studied a method for obtaining a release film having excellent releasability without wrinkles or irregularities even when used as a vehicle decorative adhesive sheet, and a laminated film using the release film. As a result, the present invention has been completed by using a base film having an elongation within a certain range under specific conditions as a release film.

That is, the gist of the present invention is as follows.
[1] It is characterized by containing a base film showing elongation (i) in the following range when subjected to thermomechanical analysis under the following conditions, and having a release layer on at least one surface of the base film. Release film for decorative adhesive sheets.
<Conditions>
Specimen size: width 4 mm x length 40 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 10 ° C / min (start temperature: 23 ° C, end temperature: 240 ° C)
Load: 400mN
<Elongation (i)>
Absolute value of elongation of base film at 125 ° C is 40 μm or less
[2] The release film for a vehicle decorative pressure-sensitive adhesive sheet according to [1], wherein the release layer is a layer made of a resin composition containing a melamine resin.
[3] The release film for a vehicle decorative adhesive sheet according to [1] or [2], wherein the base film is a polyester resin film.
[4] The release film for a vehicle decorative adhesive sheet according to [3], wherein the polyester-based resin film is a polyethylene terephthalate resin film.
[5] The release film for a vehicle decorative adhesive sheet according to any one of [1] to [4], wherein the surface roughness (Rz) of the base film is 1.20 μm or less.
[6] A laminated film for a vehicle decorative sheet, which comprises the release film for the vehicle decorative adhesive sheet according to any one of [1] to [5].
[7] The release for the vehicle decorative adhesive sheet according to any one of the polyurethane resin layer (A layer), the acrylic resin layer (B layer), and [1] to [5] on at least one surface of the original film. Lamination for vehicle decorative adhesive sheet having a mold film in the order of raw film / A layer / B layer / release film for vehicle decorative adhesive sheet (the release layer of the release film is arranged on the B layer side). the film.
[8] The vehicle addition according to [7], wherein the polyurethane-based resin layer (layer A) comprises a reaction-cured product of a polyol having at least either a polyester skeleton or a polycarbonate skeleton and a polyfunctional aliphatic isocyanate. Laminated film for decorative adhesive sheets.
[9] The vehicle decorative adhesive sheet according to [7] or [8], wherein the acrylic resin layer (B layer) is a cured product of a composition containing an acrylic polyol, a caprolactone polyol, and an isocyanate-based cross-linking agent. Laminated film.
[10] The laminated film for a vehicle decorative adhesive sheet according to [9], wherein the acrylic polyol has a hydroxyl value of 50 mgKOH / g or more.
[11] The laminated film for a vehicle decorative pressure-sensitive adhesive sheet according to [9] or [10], wherein the weight average molecular weight (Mw) of the caprolactone polyol is less than 500.
[12] The adhesive layer is provided on the surface opposite to the surface on which the A layer of the original film of the laminated film for the vehicle decorative adhesive sheet according to any one of [7] to [11] is arranged. Vehicle decoration adhesive sheet.

According to the present invention, there is provided a laminated film or adhesive sheet for a vehicle decoration adhesive sheet, which has excellent appearance with few wrinkles and irregularities over the entire film when used for a laminated film or adhesive sheet for vehicle decoration. It is possible to obtain a release film having excellent releasability. Further, by using the release film of the present invention, the film has a laminated film for a vehicle decorative sheet, which has high gloss and good scratch resistance, curved surface followability, sticking workability, etc., and the film has an adhesive layer. Adhesive sheets for vehicle decoration can be provided.

The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

1. 1. Release film for vehicle decorative adhesive sheet The release film for vehicle decorative adhesive sheet of the present invention (hereinafter, also referred to as "release film of the present invention") is as follows when subjected to thermomechanical analysis under the following conditions. It contains a base film showing the elongation (i) in the range of (i), and has a release layer on at least one side of the base film.
Since the release fill of the present invention has an elongation in the following range, it is possible to provide a laminated film for a vehicle decorative adhesive sheet having a beautiful appearance with less wrinkles and irregularities caused by the influence of heat shrinkage. It is suitably used for decorative purposes.

<Conditions>
Specimen size: width 4 mm x length 40 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 10 ° C / min (start temperature: 23 ° C, end temperature: 240 ° C)
Load: 400mN
Thermomechanical analysis can be measured using a thermomechanical analyzer TMA7100 manufactured by Hitachi High-Tech Science Corporation.
<Elongation (i)>
Absolute value of elongation of base film at 125 ° C is 40 μm or less

[Base film]
The release film of the present invention requires that the absolute value of the elongation (i) of the base film at 125 ° C. is 40 μm or less.
The present inventor has produced laminated films for vehicle decorative pressure-sensitive adhesive sheets using various release films, but in the step of laminating the release layer to the base film, which will be described later, the base film is heated by heat. Wrinkles and dents are generated due to elongation and contraction, and wrinkles and dents are transferred to the laminated film for vehicle decoration adhesive sheet (hereinafter, also simply referred to as "laminated film") obtained due to this. I found a relationship.
Since the release film of the present invention satisfies the elongation in the above range, the influence of wrinkles and dents generated by the expansion and contraction of the base film due to heat is small even in the process of laminating the release layers described later. Therefore, the appearance of the obtained laminated film for the vehicle decoration adhesive sheet can be kept good. The absolute value of such elongation is preferably 30 μm or less, more preferably 20 μm or less.

Further, since the gloss of the release film is transferred to the obtained laminated film as it is, it is preferable that the surface of the base film used for the release film is as smooth as possible. Therefore, the surface roughness (Rz) indicating the smoothness of the surface of the base film of the release film of the present invention is 1.20 μm or less, preferably 1.15 μm or less, and more preferably 1.10 μm or less. When the surface roughness of the base film is 1.20 μm or less, a laminated film having a high gloss appearance can be obtained, which is more preferable.

As the base film used in the present invention, a known one can be used as long as it satisfies the above elongation (i). For example, polyester-based resin, polyamide-based resin, fluorine-based resin, polyetherketone, polyetheretherketone, polyphenylene sulfide, polyetherimide and the like can be mentioned.

Above all, from the viewpoint of transparency, smoothness, and availability, it is preferable to use a film made of polyester resin. The polyester-based resin constituting the polyester-based resin film is a polyester-based resin composed of an aromatic dicarboxylic acid component and a diol component, and is preferably a crystalline linear saturated polyester. For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate can be mentioned.

The polyester resin may be a copolymer in which the constituent components are substituted with other components, or may be a mixture in which other polymers are mixed, for example, a mixture with polyalkylene glycol. May be good.

When it is a base film using a polyester resin, it is preferably a biaxially stretched film. Biaxial stretching can be performed by a known method. For example, the polyester is dried and then melted, extruded from a die (eg, T-die, I-die) onto a cooling drum and rapidly cooled to obtain an unstretched film. Subsequently, the unstretched film is stretched in the vertical direction in the range of 2 to 5 times, then stretched in the horizontal direction in the range of 2 to 5 times, and further heat-fixed at 160 to 260 ° C. In this way, a biaxially stretched film can be produced.

The thickness of the base film is preferably 30 μm or more and 125 μm or less from the viewpoint of film handleability and economy. If the thickness of the base film is 30 μm or more, it is possible to suppress shrinkage during the process of laminating the release layers, which will be described later, and if it is 125 μm or less, economic efficiency and good film handling are maintained. Is possible.

The base film may contain a lubricant in order to improve the slipperiness and processability of the film. Examples of the lubricant include inorganic fine particles such as calcium carbonate, kaolin, silica, and titanium oxide. Further, the base film may contain other additives such as a stabilizer, an ultraviolet absorber, a flame retardant, and an antistatic agent.
For applications requiring a matte appearance, a matte polyester film is used, preferably a polyester film containing an inorganic pigment is used, and pigments such as titanium oxide and silica can be exemplified as the inorganic pigment.

[Release layer]
In the present invention, it is necessary to provide a release layer on the base film. The release layer in the present invention exists between the base film and the acrylic resin layer (B layer) serving as the transfer foil of the vehicle decorative adhesive sheet, and is a polyurethane resin layer (B layer) on the raw film. This layer is intended to easily peel off the base film after transferring the acrylic resin layer (B layer) to the A layer). The material that imparts releasability is not particularly limited, and a known releasable agent can be used.

Examples of known mold release agents include silicone-based resins, fluororesins, and melamine resins. Above all, it is preferable to use a melamine resin from the viewpoint of releasability from the acrylic resin layer (B layer) described later and the influence on the appearance.

Examples of the melamine resin include melamine formaldehyde resin, methylated melamine formaldehyde resin, butylated melamine formaldehyde resin, and etherified melamine formaldehyde resin. A methylated melamine formaldehyde resin is preferable from the viewpoint of repelling the coating liquid when forming the B layer on the release layer and blocking when the release film is peeled off. The release layer is formed by removing the solvent and curing reaction by applying it on the base film and then heating and drying it.

When the release layer is made of a two-component curable melamine resin composed of a main agent and a curing agent, the mixing ratio of the main agent and the curing agent is preferably in the range of 90: 10 to 50:50 by weight. When the mixing ratio of the curing agent is less than 10% by mass or 50% by mass or more, the release layer may not be able to be separated from the B layer when the release film is peeled off.

The temperature at which the melamine resin is heat-dried and cured is preferably set to 120 ° C. or higher and 160 ° C. or lower. If the temperature is 120 ° C. or higher, the melamine resin can be sufficiently cured, and if the temperature is 160 ° C. or lower, the influence of shrinkage due to heat of the base film can be suppressed. It is more preferably 120 ° C. or higher and 150 ° C. or lower, and further preferably 120 ° C. or higher and 140 ° C. or lower.

The thickness of the release layer is 0.1 μm or more, preferably 0.2 μm or more, more preferably 0.3 μm or more, and 1 μm or less, preferably 0.9 μm or less, still more preferably 0.8 μm or less. If it is too thin, the releasability deteriorates, and if it is too thick, the release layer becomes uneven and the appearance of the release film deteriorates.

2. Laminated film for vehicle decorative adhesive sheet [raw film]
A known material can be used as the raw film used for the laminated film of the present invention. The material is not particularly limited, and a thermoplastic resin, a thermosetting resin, or the like can be appropriately selected and used. From the viewpoint of easy availability and handleability of the resin, it is preferable to use a thermoplastic resin.

Specific examples of the thermoplastic resin include polyolefin resins, polyvinyl chloride resins, styrene resins, acrylic resins, polyester resins, polycarbonate resins and the like.

Above all, it is preferable to use a polyolefin resin or a polyvinyl chloride resin from the viewpoint of easy availability, handleability, and economy.
When a polyolefin-based resin is used, the content of the polyolefin-based resin is preferably 50 to 100% by mass because various performances such as followability to a curved surface are improved. Examples of the polyolefin-based resin include polyethylene-based resins, polypropylene-based resins, and mixtures thereof.

Examples of the polyethylene-based resin include a homopolymer of ethylene, a copolymer of ethylene containing ethylene as a main component and another monomer copolymerizable (low-density polyethylene (LDPE), high-pressure low-density polyethylene, linear). Low-density polyethylene (LLDPE), high-density polyethylene (HDPE), ethylene-α-olefin copolymer (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst), and a mixture of two or more of these. It can be exemplified.

Examples of the polypropylene-based resin include a propylene homopolymer, a propylene copolymer, a reactor-type polypropylene-based thermoplastic elastomer, and a mixture of two or more of these. The polypropylene-based resin used in the present invention preferably has a tensile elastic modulus of 50 to 900 MPa, particularly preferably 100 to 700 MPa.

Examples of the propylene copolymer include a random copolymer (random polypropylene) and a block copolymer (block polypropylene) of propylene and ethylene or other α-olefins, a block copolymer containing a rubber component, or a graft copolymer. And so on. As the other α-olefin copolymerizable with propylene, those having 4 to 12 carbon atoms are preferable, and for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4 -Methyl-1-pentene, 1-decene and the like are mentioned, and one kind or a mixture of two or more kinds thereof is used.

Further, it is also possible to add a resin other than the polyolefin resin in the range of 0 to 50% by mass. Examples of the resin that can be added include polyesters such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as ethylene-methyl acrylate copolymers, ethylene-methacrylic acid copolymers and ethylene-methyl methacrylate copolymers, and ionomers. Examples thereof include polyvinyl chloride, polyurethane, polyamide, ethylene-vinyl alcohol copolymer, and styrene-based elastomer.
From the viewpoint of compatibility with the polyolefin resin and the mechanical properties of the obtained film, it is preferable to use a styrene elastomer.

The styrene-based elastomers include aromatic vinyl polymer blocks, butadiene polymer blocks, isoprene polymer blocks, butadiene / isoprene copolymer blocks, hydrogenated butadiene polymer blocks, and hydrogenated isoprene polymer blocks. Selected from hydrogenated butadiene / isoprene copolymer blocks, partially hydrogenated butadiene polymer blocks, partially hydrogenated isoprene polymer blocks and partially hydrogenated butadiene / isoprene copolymer blocks. It is a block copolymer with at least one kind.

When a polyvinyl chloride resin is used, a polyvinyl chloride resin having an arbitrary average degree of polymerization can be used. Preferably, the average degree of polymerization of the polyvinyl chloride resin is 600 to 3,000. When the average degree of polymerization is 600 or more, sufficient mechanical strength can be obtained. On the other hand, if the average degree of polymerization exceeds 3,000, the workability (fluidity) is significantly reduced, but the mechanical properties are not improved, which is not practical.
Therefore, from such a viewpoint, the average degree of polymerization of the polyvinyl chloride resin is particularly preferably 700 or more, more preferably 2,900 or less, and among them, 800 or more and 2,800 or less. Is more preferable.

Examples of the polyvinyl chloride-based resin include a copolymer of polyvinyl chloride (referred to as "polyvinyl chloride-based homopolymer") and a copolymer of polyvinyl chloride and a copolymerizable monomer (hereinafter, referred to as "polyvinyl chloride-based homopolymer"). "Polyvinyl chloride-based copolymer"), a graft copolymer obtained by graft-copolymerizing vinyl chloride with a polymer other than this polyvinyl chloride-based copolymer (hereinafter referred to as "polyvinyl chloride-based graft copolymer"). And so on.

Since the mechanical properties of a polyvinyl chloride-based copolymer deteriorate as the content of structural units other than the vinyl chloride monomer in the copolymer increases, vinyl chloride monopoly in the polyvinyl chloride-based copolymer The proportion of the polymer is preferably 60 to 99% by mass. The monomer copolymerizable with polyvinyl chloride may be any monomer having a reactive double bond in the molecule.

The polyvinyl chloride-based homopolymer and the polyvinyl chloride-based copolymer can be polymerized by any method, for example, an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like.

Further, the polyvinyl chloride resin may contain a plasticizer as needed. Examples of the plasticizer include phthalate-based plasticizers such as di-2-ethylhexylphthalate, di-n-octylphthalate, diisodecylphthalate, dibutylphthalate, and dihexylphthalate; dioctyl adipate, diisononyl adipate, diisodecyl adipate, and the like. Adipic acid esters such as dibutoxyethyl adipate and bis adipate (butyltriglycol) and adipic acid plasticizers typified by polyester adipate; epoxy plasticizers such as epoxidized flaxseed oil and liquid epoxy resin; triphenyl Phthalate-based plasticizers such as phosphate, trixysilyl phosphate, tricresyl phosphate; other plasticizers such as dioctyl sevacate, trimellitic acid ester, citric acid ester, benzoic acid ester, polyester-based plasticizer may be mentioned. it can.

Various additives can be added to the raw film used in the present invention, if necessary. Examples of the additive include an antistatic agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a lubricant, an antiblocking agent, a colorant and the like.

In the raw film used in the present invention, the surface of the film is easily adhered in order to improve the adhesion to a coating film layer such as a polyurethane resin layer (A layer), an adhesive layer, a primer layer and the like. Can be done.

Examples of the easy-adhesion treatment include known methods such as corona discharge treatment, plasma treatment, ozone treatment, and flame treatment.

The thickness of the raw film used in the present invention is 80 μm or more, preferably 85 μm or more, more preferably 90 μm or more, and the upper limit is not particularly limited, but is preferably 1 mm or less, more preferably 800 μm or less, still more preferably. It is 700 μm or less.
If it is too thin, it may pick up irregularities on the surface of the adherend when they are bonded together, resulting in poor appearance. From the viewpoint of film handling, it is preferable to use a raw film within the above range.
The raw film may be a single layer, a multilayer film, or a composite film.

[Polyurethane resin layer (A layer)]
The laminated film of the present invention has a polyurethane-based resin layer (A layer) on at least one side of the raw film.
The polyurethane resin layer (layer A) is a composition containing a polyurethane resin obtained by reacting an organic diisocyanate, a high molecular weight polyol, and a chain extender as a main component, and also containing a light stabilizer and an ultraviolet absorber. It is a coating layer made of a cured product.

Examples of the organic diisocyanate used in the production of the polyurethane resin obtained by reacting the above organic diisocyanate, high molecular weight polyol, and chain extender include hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like. Alicyclic diisocyanates such as diisocyanate diisocyanate, isophorone diisocyanate (IPDI), 4,4'-methylenebis (cyclohexylisocyanate) (H12MDI), ω, ω'-diisocyanate dimethylcyclohexane and other alicyclic diisocyanates, xylylene diisocyanate, tetramethyl Aromatic diisocyanates such as xylylene diisocyanate, p-phenylenediisocyanate, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate, trizine diisocyanate, and mixtures of two or more of these. Can be mentioned.
Among these, a polyfunctional aromatic diisocyanate is preferable when the mechanical strength of the coating film layer is important, and a polyfunctional aliphatic diisocyanate, particularly isophorone diisocyanate, is preferable when the weather resistance is important.

Examples of the high molecular weight polyol include polycarbonate glycol (diol) having a polycarbonate skeleton, polyol having a polyester skeleton such as polyether glycol, polyether ester glycol, and polyester glycol, polyolefin polyol such as polyolefin glycol, and silicon polyol. Polycarbonate glycol is preferred. Examples of the polycarbonate glycol include polybutylene carbonate glycol, polyhexamethylene carbonate glycol, and poly (3-methyl-1,5-pentylene) carbonate glycol obtained by deglycolation or dealcoholization from a low molecular weight diol and an alkylene carbonate or a dialkyl carbonate. Can be mentioned. Examples of the polyether glycol include those obtained by ring-opening polymerization of cyclic ether, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the polyether ester glycol include those obtained by ring-opening polymerization of cyclic ether on polyester glycol, those obtained by polycondensing polyether glycol and dicarboxylic acid, for example, poly (polytetramethylene ether) adipate and the like. As polyester glycol, dicarboxylic acid (succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, etc.) or its anhydride and low molecular weight diol (ethylene glycol, diethylene glycol, triethylene glycol, etc. Propropylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl -1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexaneglycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylolheptan, 1,9- Nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, bishydroxyethoxybenzene, etc.) obtained by polycondensation, such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, poly Examples thereof include those obtained by ring-opening polymerization of a lactone on a low molecular weight diol such as butylene sebacate, such as polycaprolactone and polymethylvalerolactone. Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol. Examples of the silicon polyol include polydimethylsiloxane polyol. As the high molecular weight polyol, two or more of the above-mentioned ones may be mixed and used.

The weight average molecular weight of the high molecular weight polyol is usually 200 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 3,000. If the molecular weight is too small, the flexibility of the coating film layer is poor, and if the molecular weight is too large, the adhesion tends to decrease.

The reaction charge amount of the organic diisocyanate and the high molecular weight polyol is 1.0 to 10 in terms of NCO / OH (molar ratio), preferably 1.5 to 5. If this ratio is too small, the amount of hard segments tends to decrease and the scratch resistance of the coating film layer tends to decrease. On the other hand, if it is too large, the solubility is poor and the viscosity tends to be too high, which is not preferable.

As the chain extender, low molecular weight diol compounds usually having a molecular weight of less than 500, which are used as raw materials for polyester polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3 -Butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1 , 3-Hexacglycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylolheptan, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc. Examples thereof include alicyclic diols such as diols and cyclohexanedimethanol, aromatic diols such as xylylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate and bisphenol A, and dialkanolamines such as N-methyldiethanolamine. Further, aromatic diamines such as 2,4- or 2,6-tolylene diamine, xylylene diamine, 4,4'-diphenylmethanediamine, ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2, 2-Dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5 An aliphatic diamine such as −pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, isophoronediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane ( IPDA), 4,4'-dicyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, tricyclodecanediamine, etc. Examples thereof include low molecular weight diamine compounds such as alicyclic diamines. These chain extenders can also be used as a mixture of two or more types. In addition, some polyols such as trimethylolpropane and glycerin can also be used in combination.

Further, in the production of urethane-based resin, a terminal terminator may be used if necessary. Examples of the terminal terminator include monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol, monoethylamine, n-propylamine, diethylamine and di-n-propylamine. Examples thereof include monoamines such as di-n-butylamine, monoethanolamines, alkanolamines such as diethanolamines and the like.

As a method for forming the A layer on the raw film, each of the above components is dissolved in a known organic solvent, and if necessary, adjusted to an appropriate concentration using a diluent or the like, and bar coat, knife coat, roll coat, etc. It can be applied by a known method such as die coating or gravure roll coating, and then dried and cured by heating at 50 to 200 ° C. for several seconds to several minutes using a hot air dryer or the like. When the curing rate is slow, it is preferable to accelerate the curing reaction for several days at room temperature of, for example, 40 to 50 ° C. after coating and drying.

The thickness of the layer A thus formed is 0.2 μm, preferably 0.5 μm or more, more preferably 1 μm or more, and the upper limit is 10 μm, preferably 7 μm or less, further preferably 5 μm. If the thickness is too thin, sufficient adhesion cannot be obtained, which is not preferable. Further, if it is too thick, curl of the laminated film and cracks of the coating film layer are generated, which is not preferable.

[Acrylic resin layer (B layer)]
In the laminated film of the present invention, a polyurethane resin layer (A layer), then an acrylic resin layer (B layer), and a release film of the present invention are placed on the raw film in this order, that is, the raw film / A. It is a film laminated in the order of layer / B layer / release film of the present invention (the release layer of the release film is arranged on the B layer side). The acrylic resin layer (layer B) is composed of a cured product of a composition containing an acrylic polyol, a caprolactone polyol, and an isocyanate-based cross-linking agent.

The acrylic polyol is a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing a (meth) acrylic acid derivative monomer with another monomer, and the like at the end. It has a hydroxyl group and reacts with the isocyanate group of an isocyanate-based compound.

Examples of the (meth) acrylic acid derivative monomer having a hydroxyl group at the terminal include hydroxyethyl (meth) acrylate and hydroxyputyl (meth) acrylate.

Other monomers copolymerizable with the (meth) acrylic acid derivative monomer having a hydroxyl group at the terminal include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl ( (Meta) acrylic acid derivative monomer having an alkyl group at the end such as meta) acrylate, (meth) acrylic acid derivative monomer having a carboxyl group at the end such as (meth) acrylic acid, benzyl (meth) acrylate, cyclohexyl (meth) There is a (meth) acrylic acid derivative monomer having an aromatic ring or a cyclic structure at the terminal such as meta) acrylate. Other than the (meth) acrylic acid derivative monomer, there are styrene monomer, cyclohexylmaleimide monomer, phenylmaleimide monomer and the like. The other monomers mentioned above may themselves have a hydroxyl group at the end.
In the present specification, "(meth) acrylic acid" refers to both acrylic acid and methacrylic acid, and "(meth) acrylate" refers to both acrylate and methacrylate.

The hydroxy group of the acrylic polyol reacts with the isocyanate of the isocyanate compound to form a cured film having a larger molecular weight, thereby exhibiting high interlayer adhesion and water vapor barrier property or oxygen barrier property. The hydroxyl value of the acrylic polyol is preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, and even more preferably 80 mgKOH / g or more. The upper limit of the hydroxyl value of the acrylic polyol is 300 mgKOH / g or less, more preferably 270 mgKOH / g or less, still more preferably 250 mgKOH / g or less. When the hydroxyl value is smaller than 50 mgKOH / g, the amount of reaction with the isocyanate-based compound is small, and the adhesion to the PVC-based film is not sufficiently developed. On the other hand, when the hydroxyl value is larger than 300 mgKOH / g, the amount of reaction with the isocyanate compound becomes too large, the film shrinkage of the acrylic resin layer (B layer) becomes large, and the polyurethane resin layer (A layer) is neatly laminated. It does not show sufficient barrier properties. The hydroxyl value (mgKOH / g) is an index of the amount of hydroxyl groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide required to acetylate the hydroxyl groups in 1 g of the acrylic polyol.

The molecular weight of the acrylic polyol is not particularly specified, but specifically, it is preferably 3000 or more and 200,000 or less, preferably 5000 or more and 100,000 or less.

As the caprolactone polyol, bifunctional polycaprolactone diols as shown in the following general formula (1), trifunctional polycaprolactone triols as shown in the following general formula (2), and other tetrafunctional polycaprolactone polyols may be used. it can.

As the polycaprolactone polyol in the B layer of the laminated film of the present invention, a polycaprolactone polyol having a polyfunctionality and a weight average molecular weight Mw of less than 500, preferably 470 or less, more preferably 450 or less can be preferably used. The hydroxyl value of the polycaprolactone polyol is 500 mgKOH / g or less, preferably 450 mgKOH / g or less, and more preferably 400 mgKOH / g or less. Since the caprolactone polyol is polyfunctional and has the above-mentioned weight average molecular weight and hydroxyl value, it is possible to obtain the effects of high crosslink density and high hardness and toughness of the cured product.

In the B layer of the laminated film of the present invention, the scratch resistance of the B layer can be further improved by further adding an isocyanate-based cross-linking agent to the acrylic polyol and the polycaprolactone polyol to react. Examples of the isocyanate-based cross-linking agent include those described in the A layer. For example, as monomeric isocyanates, aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexyl. There are aliphatic isocyanates such as methanediisocyanate (H12MDI), aromatic aliphatic isocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI). Further, polymers or derivatives of these monomeric isocyanates can also be used. For example, there are a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, and a biuret type reacted with biuret.

The isocyanate-based compound may be arbitrarily selected from the above-mentioned isocyanate-based compounds, polymers and derivatives thereof, and may be used alone or in combination of two or more.

In the resin composition constituting the B layer, the mass ratio of the acrylic polyol to the polycaprolactone polyol is 95/5 to 50/50, preferably 90/10 to 70/30, and more preferably 85/15 to 75/25. .. If the amount of polycaprolactone polyol is small, the scratch resistance of the B layer tends to decrease, and if the amount of polycaprolactone polyol is large, the stain resistance tends to decrease, which is not practically preferable.

The amount of the isocyanate-based cross-linking agent varies depending on the hydroxyl value of the acrylic copolymer and the polycaprolactone polyol, but usually the ratio of OH groups to NCO groups in the isocyanate-based cross-linking agent (NCO / OH) is 1.01 to 1 in molar ratio. It is preferably 10, and more preferably 1.5 to 5.
Further, polysiloxane can be mixed with the B layer for the purpose of imparting performance such as stain resistance. Examples of polysiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxy. Silane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, Partial hydrolyzate of a silane compound having a hydrolyzable silyl group such as γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, and anhydrous silicate in an organic solvent. At least one selected from an organosilica sol in which fine particles of acid are stably dispersed and one in which the above-mentioned silane compound having radical polymerizable property is added to the organosilica sol can be used.

When the B layer is formed on the A layer of the laminated film of the present invention, the composition constituting the B layer is dissolved in a known organic solvent in the same manner as when the A layer is formed on the raw fabric film, and further. If necessary, adjust to an appropriate concentration using a diluent or the like, apply by a known method such as bar coat, knife coat, roll coat, die coat or gravure roll coat, and then use a hot air dryer or the like to usually apply. It is carried out by heating at 50 to 200 ° C. for several seconds to several minutes to dry and cure. When the curing rate is slow, for example, the B layer is formed on the release layer of the releasable film of the present invention, and the B layer is laminated with the surface of the A layer of the raw film on which the A layer is formed in advance. It can also be formed on layers. After coating and drying, it is preferable to further accelerate the curing reaction for several days at room temperature of, for example, 40 to 50 ° C.

The thickness of the B layer thus formed is preferably 0.2 to 50 μm. When the thickness of the B layer is 0.2 μm or more, the raw film and the adherend can be sufficiently protected. On the other hand, if the thickness of the B layer is 50 μm or less, poor appearance due to thickness unevenness can be suppressed.

Further, in the laminated film of the present invention, an antistatic agent is added to at least one of the A layer and the B layer in consideration of secondary processability and the like, or the PVC film and A are used, as long as the performance is not impaired. An antistatic layer may be provided between the layers or between the A layer and the B layer.

Examples of the antistatic agent include nonionic antistatic agents such as polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, glycerin fatty acid ester, and sorbitan fatty acid ester; alkyl sulfonate, Anionic antistatic agents such as alkylbenzene sulfonate, alkyl sulphate and alkyl phosphate; cationic antistatic agents such as quaternary ammonium chloride, quaternary ammonium sulfate and quaternary ammonium nitrate; alkyl betaine type, alkyl imidazoline type, An amphoteric antistatic agent such as an alkylalanine type and a conductive resin such as a polyvinylbenzyl type cation and a polyacrylic acid type cation are used.

Examples of the antistatic layer include a layer in which conductive fillers such as tin oxide, indium oxide, and zinc oxide are dispersed in a binder made of an organic compound, and a layer made of a charge transfer type boron polymer resin. Be done.

Further, it is preferable to add an ultraviolet absorber and / or a hindered amine-based light stabilizer or the like to at least one of the A layer and the B layer for the purpose of imparting weather resistance outdoors for a long period of time and under harsh conditions.

The amount of the ultraviolet absorber or the hindered amine-based light stabilizer can be added in an amount of 1 to 70 parts by mass with respect to 100 parts by mass of the resin component in the A layer or the B layer, even when each is used alone or in combination, and 1 in the layer. It is preferably ~ 30% by mass. When the ultraviolet absorber and the light stabilizer are used in combination, the addition ratio thereof is not particularly limited, but usually, the ultraviolet absorber / hindered amine-based light stabilizer = about 1/3 to 3/1 (weight ratio). ..
If the amount of the ultraviolet absorber and / or the hindered amine-based light stabilizer is small, the weather resistance may be deteriorated. On the other hand, if the blending amount is too large, the solvent resistance and the scratch resistance are deteriorated, which is not preferable.

Further, a curing catalyst can be added to at least one of the A layer and the B layer for the purpose of promoting the crosslinking reaction. Examples of the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and monobutyl. Examples include organic metal compounds such as tin trioctate, lead 2-ethylhexanoate, zinc octylate and mixtures thereof. The amount of the curing catalyst used is not particularly limited, but it is usually suitable to be 0.005 to 5% by mass, particularly 0.01 to 3% by mass, in the solid content in the layer.

In addition, at least one of an antioxidant, an organic powder, and an inorganic powder may be added to at least one of the A layer and the B layer as long as the performance is not impaired.

3. 3. Vehicle decoration adhesive sheet The laminated film of the present invention is a vehicle decoration adhesive sheet (a surface on which the A layer is not formed) by forming an adhesive layer on the surface opposite to the A layer of the original film. Hereinafter, it may be simply referred to as "adhesive sheet").
By attaching the adhesive sheet of the present invention to the adherend, it is possible to impart glossiness and weather resistance to the adherend.

The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer may be either an acrylic-based pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive, but when used outdoors, an acrylic-based pressure-sensitive adhesive having high weather resistance is preferable. Examples of the monomer constituting the acrylic pressure-sensitive adhesive include (meth) acrylic acid ester monomer, and the (meth) acrylic acid ester monomer is an alcoholic (meth) acrylic acid having an alkyl group having 2 to 12 carbon atoms. An ester, preferably a (meth) acrylic acid ester having an alkyl group having 4 to 12 carbon atoms, is used, specifically n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth). ) Isooctyl acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and the like can be mentioned. These can be used alone or in combination. Due to the balance between adhesiveness and cohesiveness, the glass transition temperature (Tg) of homopolymers is usually -50 ° C or lower, and the main component is (meth) acrylic acid ester, which is a lower alcohol such as ethyl (meth) acrylate. It is preferable to use a meta) acrylic acid ester together.

In addition to these vinyl monomers, monomers copolymerizable with these may be copolymerized. Examples of such a copolymerizable monomer include a carboxyl group-containing monomer such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid or an anhydride thereof, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl acrylate. , Polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, caprolactone-modified (meth) acrylate and other hydroxyl group-containing monomers.

The pressure-sensitive adhesive may be a solvent-based acrylic pressure-sensitive adhesive polymerized in a solvent, an emulsion-based pressure-sensitive adhesive polymerized in water, or a bulk polymerization-type pressure-sensitive adhesive obtained by irradiating a monomer mixture with ultraviolet rays. Good.

The thickness of the pressure-sensitive adhesive layer varies depending on the composition of the pressure-sensitive adhesive and is not particularly limited, but is usually 10 to 50 μm.

As a method for forming the pressure-sensitive adhesive layer on the laminated film in the pressure-sensitive adhesive sheet of the present invention, a known method can be used. For example, the above adhesive or the like is dissolved in a known organic solvent, and if necessary, a diluent or the like is used to adjust the concentration to an appropriate level, and a bar is used as a separator (for example, a release material such as a release paper coated with silicon). A known method such as a coat, a knife coat, a roll coat, a die coat or a gravure roll coat is applied to the surface of the raw film opposite to the surface on which the A layer is formed, and then dried using a hot air dryer or the like. The pressure-sensitive adhesive layer can be formed by a method such as allowing the adhesive layer to be formed.

Further, the pressure-sensitive adhesive sheet of the present invention contains a primer containing at least one selected from the group consisting of an acrylic resin, a urethane resin, and an acrylic-modified urethane resin in order to improve adhesion between the raw film and the pressure-sensitive adhesive layer. A layer may be provided.

In the pressure-sensitive adhesive sheet of the present invention, the gloss value of the B layer after peeling the release film is 80 or more, preferably 85 or more, and more preferably 90 or more. In particular, when a resin composition containing a melamine resin as the release layer is used, the gloss value is good.

[Use of the present invention]
The release film, laminated film, and adhesive sheet of the present invention are used for decorative adhesive labels for imparting design to vehicles such as automobiles. The vehicle referred to in the present invention includes a bicycle, a motorcycle, a tricycle, an automobile, a truck, an aircraft, a ship, and the like.

Hereinafter, examples and comparative examples of the present invention will be shown and specifically described, but the present invention is not limited to these examples. The materials used in the following examples and comparative examples, the method for measuring the evaluated characteristics, and the like are as follows.

[Material used]
<Polyolefin resin>
Resin A: "F327" manufactured by Prime Polymer Co., Ltd. (random polypropylene, Tm: 140 ° C)
Resin B: "Novatec FY6HA" manufactured by Japan Polypropylene Corporation (homopolypropylene, Tm: 168 ° C)
Resin C: "Tough Tech H1221" manufactured by Asahi Kasei Chemicals Co., Ltd. (hydrogenated styrene elastomer)

<Polyvinyl chloride resin>
Resin D: "TH-1000" manufactured by Taiyo PVC Co., Ltd. (average degree of polymerization: 1000)

<Additives, etc.>
-Polyester plasticizer: "D643" manufactured by J-PLUS Co., Ltd. (Mw: 1800)
-Colorant (α): PO-based masterbatch containing 20% by mass of carbon black manufactured by Toyo Ink Co., Ltd.-Colorant (β): "DA MKV 994 Black" (carbon black) manufactured by Dainichiseika Kogyo Co., Ltd.
-Light stabilizer: BASF's "Chimassorb 944" (hindered amine-based light stabilizer)
-Heat stabilizer: (ADEKA's "ADEKA ZTAB (registered trademark) SP-2005" (magnesium-zinc heat stabilizer)
-Ultraviolet absorber: "Chimassorb81" manufactured by BASF (benzophenone-based ultraviolet absorber)

<Resin composition for polyurethane resin layer (A layer)>
Polycarbonate urethane resin: "My Tech (registered trademark) AE870" manufactured by Mitsubishi Chemical Corporation

<Resin composition for acrylic resin layer (B layer)>
A mixture with the following compounding ratio was used.
Acrylic polyol resin: Hitachi Kasei Co., Ltd. "Hitaroid (registered trademark) D1002" (hydroxyl value 200 mgKOH / g) 60% by mass
Caprolactone polyol: Daicel's "Plaxel (registered trademark) FM1D" (molecular weight 358) 10% by mass
HDI: Asahi Kasei "Duranate (registered trademark) TPA100" 30% by mass

<Base film for release film>
Base film (G): "Diafoil (registered trademark) T600-50" manufactured by Mitsubishi Chemical Corporation (polyester resin film, 50 μm)
Base film (H): "Cosmo Shine (registered trademark) E5001" manufactured by Toyobo Co., Ltd. (polyester resin film, 50 μm)
Base film (I): "Emblet (registered trademark) S50" manufactured by Unitika Ltd. (polyester resin film, 50 μm)
Base film (J): "Lumirror (registered trademark) T60 # 100" manufactured by Toray Industries, Inc. (polyester resin film, 100 μm, elongation (i) -6 μm)
Base film (K): "Lumirror (registered trademark) T60 # 50" manufactured by Toray Industries, Inc. (polyester resin film, 50 μm, elongation (i) 45 μm)

<Resin composition for release layer>
Resin composition (P): A mixture of 100 parts by mass of a methylated melamine resin (“RP-30” manufactured by Sasaki Paint Co., Ltd.) and 10 parts by mass of a curing agent (“CP catalyst” manufactured by Sasaki Paint Co., Ltd.). (Q): Silicon-modified acrylic resin ("AB002" manufactured by Sasaki Paint Co., Ltd.)
Resin composition (R): Polyester resin ("HZ-523" manufactured by Takamatsu Oil & Fat Co., Ltd.)

(1) Film formation of polyolefin-based resin film (raw film) Each resin is dry-blended according to the formulation shown in Table 1 and put into the hopper of a single-screw extruder (50φ mm, L / D = 32) manufactured by Toshiba Machine Co., Ltd. Then, the extruder temperature was adjusted between 190 ° C. and 230 ° C., and the mixture was extruded from a 550 mm wide T-die (temperature setting: 230 ° C., lip opening degree 0.8 mm). The extruded molten resin was cooled and solidified by a winder equipped with a cooling roll (cooling roll 700 mm width × φ350 mm, roll temperature 30 ° C.) to prepare a polyolefin-based resin film having a thickness of 100 μm.

(2) Formation of Polyurethane Resin Layer (A Layer) On the polyolefin resin film obtained in (1), the resin composition for the polyurethane resin layer (A layer) is coated by the reverse coating method after drying. The coating was applied so that the amount was 1 μm.

(3) Formation of release film A release layer is obtained by applying various release layer resin compositions on a base film for various release films by a reverse coating method so that the coating amount after drying is 0.3 μm. Was applied to obtain a release film. The drying temperature at the time of coating was 125 ° C.

(4) Formation of Acrylic Resin Layer (B Layer) and Formation of Laminated Film The resin composition for acrylic resin layer (B layer) is reverse-coated on the release layer of the release film obtained in (3). The acrylic resin layer (B layer) was coated so that the coating amount after drying was 15 μm. The layer A obtained in (2) was attached to it and stored in a constant temperature chamber at 40 ° C. for 5 days in order to promote the crosslinking reaction. After taking out from the constant temperature chamber, a laminated film (polyolefin resin / A layer / B layer / release film) was obtained.

[Measurement of tensile modulus]
A No. 1 dumbbell test piece was collected from the polyolefin-based resin film obtained in (1), and in accordance with JIS K 7127, under an atmosphere of 23 ° C. and 10 ° C., using an autograph (AGS-X manufactured by Shimadzu Corporation). The tensile elastic modulus was measured at a tensile speed of 50 mm / min.

[Measurement of Elongation (i) of Base Film]
The elongation (i) of the base film was measured using the following measuring device and conditions.
<Measurement conditions>
Equipment: Thermomechanical analyzer TMA7100
(Made by Hitachi High-Tech Science)
Specimen size: width 4 mm x length 40 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 10 ° C / min (start: 23 ° C, end: 240 ° C)
Load: 400mN

[Measurement of surface roughness (Rz)]
For the surface roughness (Rz) of the base film for the release film, SURFCOM FLEX-50A manufactured by Tokyo Seimitsu Co., Ltd. is used, and the tip of a erosion needle having a radius of 2 μm and an angle of 60 ° is used according to JIS B0601 (2001). The measurement was performed with a measuring force of 0.7 mN.

[Roll appearance of release film]
The appearance of the roll when the release film was wound up to 1000 m was visually judged according to the following criteria.
◎: No wrinkles or irregularities on the roll 〇: Slight wrinkles or irregularities are observed on the roll, but there is no problem in use ×: Wrinkles or irregularities are observed on the roll and cannot be used

[Appearance of coating when laminating acrylic resin layer (B layer)]
The appearance of the B layer when the resin composition for the acrylic resin layer (B layer) was applied onto the release layer of the release film by the reverse coating method was visually determined.
◯: The B layer is uniformly coated and the appearance is good. ×: The B layer is not uniformly coated, and defects such as repellent are observed.

[Roll appearance of laminated film]
The roll appearance when the obtained laminated film was wound up to 1000 m was visually judged according to the following criteria.
◎: No wrinkles or irregularities are observed on the roll 〇: Wrinkles or irregularities are slightly observed on the roll, but there is no problem in use. ×: Wrinkles or irregularities are noticeably observed on the roll and cannot be used.

[Blocking of release film]
Blocking when peeling the release film from the obtained laminated film was determined according to the following criteria.
◯: No blocking occurs and easy peeling possible Δ: Blocking but peelable ×: Blocking is remarkable and peeling is difficult

[Measurement of 60 ° gloss value]
Remove the release film from the laminated film, use the obtained polyolefin-based coating film, and use a portable gloss meter (GMX-203 manufactured by Murakami Color Technology Research Institute) to form the B layer in accordance with JIS K7105. The 60 ° gloss value was measured.

[Example 1]
A colorant and a stabilizer were blended with 100 parts by mass of the polyolefin resin as shown in Table 1 to obtain a polyolefin resin film under the condition (1) described above. The tensile elastic modulus of the obtained raw film was 600 MPa.
When the polyester resin film described in (G) above was used as the base film of the release film, the elongation (i) was 25 μm and the surface roughness (Rz) was 0.92 μm.
Since the elongation (i) of this base film is within a predetermined range and the influence of dimensional change due to heating is small, the roll appearance of the release film when the release layers are laminated and wound up to 1000 m. No wrinkles or irregularities were observed.
Regarding the appearance when the B layer was coated on the release film, it was confirmed that the B layer was uniformly coated without any repellency or the like.
Furthermore, no wrinkles or irregularities were observed in the roll appearance when the laminated film obtained in the order of polyolefin resin film / A layer / B layer / release film (release layer is on the B layer side) was wound up for 1000 m. It was.
The release film was removed from this laminated film, and the 60 ° gloss value on the B layer side of the obtained polyolefin-based coating film was 91, confirming that it had a good high gloss appearance. The results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was carried out except that the polyester-based resin film described in (H) above was used as the base film for the release film.
The polyester resin film according to (H) had an elongation (i) of 12 μm and a surface roughness (Rz) of 0.88 μm.
Since the elongation (i) of this base film is within a predetermined range and the influence of dimensional change due to heating is small, the roll appearance of the release film when the release layers are laminated and wound up to 1000 m. No wrinkles or irregularities were observed.
Regarding the appearance when the B layer was coated on the release film, it was confirmed that the B layer was uniformly coated without any repellency or the like.
Furthermore, no wrinkles or irregularities were observed in the roll appearance when the laminated film obtained in the order of polyolefin resin film / A layer / B layer / release film (release layer is on the B layer side) was wound up for 1000 m. It was.
The release film was removed from this laminated film, and the 60 ° gloss value on the B layer side of the obtained polyolefin-based coating film was 92, confirming that it had a good high gloss appearance. The results are shown in Table 1.

[Example 3]
The same procedure as in Example 1 was carried out except that the polyester-based resin film described in (I) described above was used as the base film.
The polyester resin film according to (I) had an elongation (i) of 3 μm and a surface roughness (Rz) of 1.15 μm.
Since the elongation (i) of this base film is within a predetermined range and the influence of dimensional change due to heating is small, the roll appearance of the release film when the release layers are laminated and wound up to 1000 m. No wrinkles or irregularities were observed.
Regarding the appearance when the B layer was coated on the release film, it was confirmed that the B layer was uniformly coated without any repellency or the like.
Furthermore, no wrinkles or irregularities were observed in the roll appearance when the laminated film obtained in the order of polyolefin resin film / A layer / B layer / release film (release layer is on the B layer side) was wound up for 1000 m. It was.
The release film was removed from this laminated film, and the 60 ° gloss value on the B layer side of the obtained polyolefin-based coating film was 88, confirming that the film had a good glossy appearance. The results are shown in Table 1.

[Example 4]
The same procedure as in Example 1 was carried out except that the raw film was as shown in Table 1.
No wrinkles or irregularities were observed on the roll appearance of either the release film or the laminated film.
The release film was removed from this laminated film, and the 60 ° gloss value on the B layer side of the obtained polyolefin-based coating film was 91, confirming that it had a good high gloss appearance. The results are shown in Table 1.

[Example 5]
The same procedure as in Example 1 was carried out except that the raw film was as shown in Table 1 and the base film used for the release film was as shown in (J).
The polyester resin film according to (J) had an elongation (i) of −6 μm and a surface roughness (Rz) of 0.92 μm.
Since the elongation (i) of this base film is within a predetermined range and the influence of dimensional change due to heating is small, the roll appearance of the release film when the release layers are laminated and wound up to 1000 m. No wrinkles or irregularities were observed.
Regarding the appearance when the B layer was coated on the release film, it was confirmed that the B layer was uniformly coated without any repellency or the like.
Furthermore, no wrinkles or irregularities were observed in the roll appearance when the laminated film obtained in the order of polyolefin resin film / A layer / B layer / release film (release layer is on the B layer side) was wound up for 1000 m. It was.
The release film was removed from this laminated film, and the 60 ° gloss value on the B layer side of the obtained polyolefin-based coating film was 92, confirming that the film had a good glossy appearance. The results are shown in Table 1.

[Example 6]
The same procedure as in Example 1 was carried out except that the raw film was as shown in Table 1.
No wrinkles or irregularities were observed on the roll appearance of either the release film or the laminated film.
The release film was removed from this laminated film, and the 60 ° gloss value on the B layer side of the obtained polyvinyl chloride-based coating film was 92, confirming that it had a good high-gloss appearance. The results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that the base film used for the release film was the one described in (K).
The polyester resin film according to (K) had an elongation (i) of 45 μm and a surface roughness (Rz) of 0.98 μm.
The elongation (i) of this base film exceeds the upper limit of the predetermined range, and the influence of the dimensional change due to heating is large. Occurrence of wrinkles and unevenness was confirmed.
Further, wrinkles and irregularities were observed in the roll appearance when the laminated film obtained in the order of polyolefin resin film / A layer / B layer / release film (release layer is on the B layer side) was wound up for 1000 m. Transfer of wrinkles and irregularities was also confirmed on the polyolefin-based coating film.

[Reference example 1]
The same procedure as in Example 1 was carried out except that the resin composition for the release layer was as shown in Table 1.
It was confirmed that the B layer was not uniformly coated on the obtained release film, and cissing and unevenness were observed, and the appearance was inferior.
No wrinkles or irregularities were observed in the roll appearance when the laminated film obtained in the order of polyolefin resin film / A layer / B layer / release film (release layer is on the B layer side) was wound up for 1000 m. Blocking was confirmed between the B layer and the release film, which was inferior in releasability.

[Reference example 2]
The same procedure as in Example 1 was carried out except that the resin composition for the release layer was as shown in Table 1.
Wrinkles and irregularities were observed in the roll appearance when the laminated film obtained in the order of the release film and the polyolefin resin film / A layer / B layer / release film (the release layer is on the B layer side) was wound up for 1000 m. However, remarkable blocking was confirmed between the B layer and the release film, and peeling was difficult.

[Example 7]
Acrylic adhesive (SK Dyne 1502C manufactured by Soken Kagaku Co., Ltd.) is applied on the separator by the comma coating method so that the thickness of the adhesive layer after drying is 25 μm, and it is put into a hot air dryer at 80 ° C. After drying for 5 minutes, a pressure-sensitive adhesive layer was formed to obtain a separator with a pressure-sensitive adhesive layer.
A vehicle decorative adhesive sheet was obtained by laminating the surface of the pressure-sensitive adhesive layer of the separator with a pressure-sensitive adhesive and the surface of the laminated films of Examples 1 to 6 opposite to the layer A.
None of the obtained adhesive sheets showed good appearance with no wrinkles or irregularities observed on the surface.

As described above, according to the configuration of the present invention, a release film having excellent releasability with few wrinkles and irregularities even when used for vehicle decoration, and a high gloss and scratch resistance using the releasable film. It is possible to provide a laminated film suitable for various uses, including a marking film having good curved surface followability, sticking workability, and the like.

According to the configuration of the present invention, a release film having no wrinkles or irregularities and having excellent releasability even when used for vehicle decoration, and a high gloss using the releasable film, scratch resistance, and curved surface followability. It is possible to provide a laminated film suitable for various uses, including a marking film having good sticking workability and the like.

Claims (12)

A vehicle decorative adhesive characterized by containing a base film showing elongation (i) in the following range when subjected to thermomechanical analysis under the following conditions and having a release layer on at least one side of the base film. Release film for sheets.
<Conditions>
Specimen size: width 4 mm x length 40 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 10 ° C / min (start temperature: 23 ° C, end temperature: 240 ° C)
Load: 400mN
<Elongation (i)>
Absolute value of elongation of base film at 125 ° C is 40 μm or less The release film for a vehicle decorative pressure-sensitive adhesive sheet according to claim 1, wherein the release layer is a layer made of a resin composition containing a melamine resin. The release film for a vehicle decorative pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the base film is a polyester-based resin film. The release film for a vehicle decorative adhesive sheet according to claim 3, wherein the polyester-based resin film is a polyethylene terephthalate resin film. The release film for a vehicle decorative pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the surface roughness (Rz) of the base film is 1.20 μm or less. A laminated film for a vehicle decorative pressure-sensitive adhesive sheet, which comprises the release film for the vehicle decoration pressure-sensitive adhesive sheet according to any one of claims 1 to 5. A release film for a vehicle decorative adhesive sheet according to any one of a polyurethane resin layer (A layer), an acrylic resin layer (B layer), and claims 1 to 5 is placed on at least one surface of the original film. A laminated film for a vehicle decorative adhesive sheet having a film / A layer / B layer / a release film for a vehicle decorative adhesive sheet (the release layer of the release film is arranged on the B layer side) in this order. The vehicle decorative pressure-sensitive adhesive sheet according to claim 7, wherein the polyurethane-based resin layer (layer A) comprises a reaction-cured product of a polyol having at least either a polyester skeleton or a polycarbonate skeleton and a polyfunctional aliphatic isocyanate. For laminated film. The laminated film for a vehicle decorative pressure-sensitive adhesive sheet according to claim 7 or 8, wherein the acrylic resin layer (B layer) is a cured product of a composition containing an acrylic polyol, a caprolactone polyol, and an isocyanate-based cross-linking agent. The laminated film for a vehicle decorative pressure-sensitive adhesive sheet according to claim 9, wherein the acrylic polyol has a hydroxyl value of 50 mgKOH / g or more. The laminated film for a vehicle decorative pressure-sensitive adhesive sheet according to claim 9 or 10, wherein the weight average molecular weight (Mw) of the caprolactone polyol is less than 500. A vehicle decorative adhesive sheet having an adhesive layer on a surface opposite to the surface on which the A layer of the original film of the laminated film for a vehicle decorative adhesive sheet according to any one of claims 7 to 11 is arranged. ..