JP6938280B2 - Adhesive film - Google Patents

Description

The present invention relates to an adhesive film. More specifically, the present invention relates to an adhesive film suitable for wallpaper.

Conventionally, a decorative and decorated adhesive film (so-called wallpaper) is attached to the surface of a wall or ceiling of a building to make up and decorate. When installing wallpaper on a wall, etc., it is possible to install it without causing air or foreign matter to get caught between the surface of the wall, etc. and the surface of the adhesive layer of the wallpaper, causing swelling, wrinkles, or other appearance defects. Is required to do. Therefore, from the viewpoint of workability, it is preferable to divide the wallpaper into a size that is easy to work with. In addition, since the product width of the wallpaper is usually narrower than the width of the wall or ceiling of the building, it is usual to join the wallpapers together and paste them in a butt state. However, the construction is not perfect at the place where the wallpaper is jointed and butt-butted; the base film of the wallpaper shrinks; for some reason, the wallpaper and the wallpaper are separated immediately after the construction or over time after the construction. The problem is that the seams are slightly open (hereinafter, this phenomenon is sometimes called "meski"), which is conspicuous and impairs the design of the wall, etc. (hereinafter, "meski problem"). It may be called.)

Japanese Unexamined Patent Publication No. 2003-103741 Japanese Unexamined Patent Publication No. 2009-096108

An object of the present invention is to provide an adhesive film in which even if a mesh is generated, it is inconspicuous. A further problem of the present invention is that it is excellent in adhesive strength, peeling resistance, curling resistance, and bending workability, and has good workability in any of the cold winter season and the hot summer season. However, even if messiness occurs, it is intended to provide an inconspicuous adhesive film.

As a result of diligent research, the present inventor has found that the above-mentioned problems can be achieved by a specific adhesive film.

That is, the present invention is an adhesive film having an adhesive layer on one side of a film base material, and is an adhesive film satisfying the following formula (1).
-26 ≤ (L1-L2) ≤ 4 ... (1)
Here, L1 is the brightness in the L * a * b * coordinates of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film.
L2 is the brightness at the L * a * b * coordinates of the front surface of the adhesive film in the actual use state.

In the second invention, the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is
(A) 100 parts by mass of an acrylic polymer satisfying the following characteristics (a1) and (a2);
(B) Compound having two or more isocyanate groups in one molecule 0.1 to 3 parts by mass;
The adhesive film according to the first invention.
(A1) The acid value is 18 to 27 mgKOH / g.
(A2) The mass average molecular weight is 500 to 1,000,000.

The third invention is the adhesion according to the first invention or the second invention, wherein the tackiness of the surface of the pressure-sensitive adhesive layer at a temperature of 5 ° C. is 12 to 25 N, and the tackiness at a temperature of 35 ° C. is 12 to 23 N. It is a film.

The fourth invention is the adhesive film according to any one of the first to third inventions for wallpaper.

In the adhesive film of the present invention, even if a mesh is generated, it is not noticeable. The preferable adhesive film of the present invention is excellent in adhesive strength, peeling resistance, curling resistance, and bending workability, and has good workability in any of the cold winter season and the hot summer season. However, even if mess is generated, it is not noticeable. Therefore, it can be suitably used as a so-called wallpaper for decorating and decorating the walls and ceilings of buildings.

As used herein, the term "film" is used interchangeably or interchangeably with "sheet". The term "resin" is used as a term that also includes a resin mixture containing two or more resins and a resin composition containing a component other than the resin. Further, in the present specification, laminating a certain layer and another layer in order means directly laminating those layers and interposing one or more other layers such as an anchor coat between the layers. Includes both stacking. The term "greater than or equal to" related to a numerical range is used to mean a certain numerical value or a certain numerical value or more. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Furthermore, the "~" symbol related to the numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, greater than 10% and less than 90%, or 90%. The term "film" is used as a term that also includes sheets. Except in the examples, or unless otherwise specified, all numbers used herein and in the claims should be understood as being modified by the term "about". Without attempting to limit the application of the doctrine of equivalents to the claims, each number should be interpreted in the light of significant figures and by applying conventional rounding techniques.

The pressure-sensitive adhesive film of the present invention is a pressure-sensitive adhesive film having an pressure-sensitive adhesive layer on one side of a film base material, and satisfies the following formula (1).
-26 ≤ (L1-L2) ≤ 4 ... (1)
Here, L1 is the brightness at the L * a * b * coordinates of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, and L2 is the brightness at the L * a * b * coordinates of the front surface of the pressure-sensitive adhesive film in the actual use state. ..

By satisfying the above formula (1), the adhesive film of the present invention makes even if a mesh is generated, it becomes inconspicuous. The value of (L1-L2) is usually −26 or more, preferably -25 or more, more preferably -24 or more, from the viewpoint of making the meshi inconspicuous even if it occurs. Further, it is usually 4 or less, preferably 3 or less, more preferably 2 or less, and further preferably 1 or less.

Even if a mess is generated, it is truly surprising that the above equation (1) should be satisfied in order to make it inconspicuous. FIG. 1 shows the saturation (C1) calculated from the L * a * b * coordinates of the pressure-sensitive adhesive layer on the horizontal axis and the L * a * of the front surface of the pressure-sensitive adhesive film in the actual use state. The value of the difference (C1-C2) from the saturation (C2) calculated from the b * coordinates is taken as the value of the above (L1-L2) on the vertical axis. Those with ○ evaluation are ○ plots, those with △ evaluation are △ plots, and those with × evaluation are □ plots. From FIG. 1, it can be intuitively read that the inconspicuousness of Meski is uniquely determined by the above values (L1-L2) regardless of the difference in saturation.

In the present specification, the "actual use state" means a state in which the adhesive film of the present invention is applied to the wall or ceiling in order to decorate or decorate the wall or ceiling of the building. The front surface of the adhesive film in the actual use state is usually a visible surface in the constructed state.

In the present specification, the L * a * b * coordinates of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film are geometrical using the spectrophotometer "CM600d (trade name)" of Konica Minolta Japan Co., Ltd. in accordance with JIS Z8722: 2009. It was calculated by measuring the XYZ coordinates under the condition c and the condition including the component that becomes the mirror surface reflection, and converting this into the L * a * b * coordinates.

In the present specification, the L * a * b * coordinates of the front surface of the adhesive film in the actual use state are the spectrophotometer "CM600d (trade name)" of Konica Minolta Japan Co., Ltd. in accordance with JIS Z8722: 2009. Was used to measure the XYZ coordinates under the conditions including the geometric condition c and the component that causes mirror reflection, and this was calculated by converting them into the L * a * b * coordinates.

For the L * a * b * coordinates, you can refer to the homepage of Konica Minolta Japan Co., Ltd. (address below).
http://www.konicaminolta.jp/instruments/knowledge/color/part1/07.html

When the color of the front surface is not uniform in the actual use state of the adhesive film, for example, when the pattern is printed, L when the pattern on the measurement surface is uniform. The * a * b * coordinates are used as the L * a * b * coordinates of the front surface of the adhesive film in the actual use state.

For example, when the pattern is a patchwork of a red circle on a blue background, the area ratio of the blue background is 70%, and the area ratio of the red circle is 30%, L * a on the blue background. The * b * coordinates and the L * a * b * coordinates of the red circle may be measured, and the average value of the L * a * b * coordinates may be calculated in consideration of the area ratio of each.

For example, when the pattern is a gradation, a sample having a size that fully considers the periodicity of the gradation is cut out from the adhesive film and divided into a large number of measurement pieces having the same shape (usually 20 or more). , Preferably 50 or more), and the average value may be calculated by measuring the L * a * b * coordinates at one randomly determined location for each measurement piece. For example, when the gradation pattern is applied using a gravure roll, the length of the sample in the machine direction is preferably one round of the gravure roll.

1. 1. Adhesive:
From the viewpoint of making the meshi inconspicuous, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention is a predetermined surface color (L * a * b * coordinates) that is normally visible on the front surface in the actual use state of the pressure-sensitive adhesive film. It has a color (L * a * b * coordinates).

The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention is not limited except that it has a predetermined color, and any pressure-sensitive adhesive can be used.

Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, vinyl acetate-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Among these, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive. As the pressure-sensitive adhesive, one kind or a mixture of two or more kinds of these can be used.

The adhesive is an acrylic polymer that satisfies (A) the following properties (a1) and (a2) from the viewpoint of imparting good workability in both the cold winter season and the hot summer season. And (B) a mixture with a compound having two or more isocyanate groups in one molecule is more preferable.
(A1) The acid value is 18 to 27 mgKOH / g.
(A2) The mass average molecular weight is 500 to 1,000,000.

The component (A) is an acrylic polymer. The component (A) exhibits adhesiveness as the main component of the pressure-sensitive adhesive, and also functions to include the component (B) and other optional components.

The acid value of the component (A) may be usually 27 mgKOH / g or less, preferably 26 mgKOH / g or less, and more preferably 25 mgKOH / g or less, from the viewpoint of improving the enforceability in the cold winter season. On the other hand, from the viewpoint of initial adhesive strength, prevention of peeling, prevention of turning over, and prevention of generation of mess, it may be usually 18 mgKOH / g or more, preferably 20 mgKOH / g or more, and more preferably 22 mgKOH / g or more.

In the present specification, the acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the sample, and is the 3.1 neutralization titration method of JIS K0070-1992. It is a value measured according to.

The mass average molecular weight of the component (A) may be usually 500,000 or more, preferably 550,000 or more, from the viewpoint of imparting appropriate hardness to the pressure-sensitive adhesive and preventing peeling, turning, and generation of mess. .. On the other hand, from the viewpoint of coatability, it may be usually 1 million or less, preferably 800,000 or less.

In this specification, the mass average molecular weight was determined using gel permeation chromatography (GPC). GPC measurement, high performance liquid chromatography system "SHODEX GPC-101 (trade name)" of Showa Denko KK, the columns and column 1 × 10 ⁴ polystyrene column (exclusion limit is 4 × 10 ⁸ coupled one each (Use) was used, and the measurement was performed under the conditions of a measurement temperature of 40 ° C., a flow velocity of 1 mL / min, tetrahydrofuran (THF) for mobile phase high-speed liquid chromatography, and a sample concentration of 1 mg / mL. The molecular weight calibration curve was created using standard polystyrene. For the theory of GPC and the actual measurement, refer to reference books such as "Size Exclusion Chromatography, High-Speed Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, 1st Edition, December 10, 1991". You can refer to it.

The glass transition temperature of the component (A) depends on the type and blending amount of the component (B) from the viewpoint of improving workability during low-temperature construction, but is preferably −50 ° C. or lower, more preferably −. It may be 55 ° C. or lower. On the other hand, from the viewpoint of maintaining the adhesive strength at a high temperature and preventing peeling, turning, and generation of mess, the temperature may be preferably −70 ° C. or higher, more preferably −60 ° C. or higher.

In the present specification, the glass transition temperature of the component (A) is a calculated value obtained by a conventional method, that is, a value obtained from the following formula (Fox's formula).
1 / (Tg + 273) = W ₁ / (Tg ₁ +273) + W ₂ / (Tg ₂ +273) + W ₃ / (Tg ₃ +273) + ... + W _n / (Tg _n +273)
In the formula, Tg is the glass transition temperature (° C.) of the polymer composed of n kinds of monomers, and W ₁ , W ₂ , W ₃ ... W _n are each single in the monomer composition. is the mass% of the _{dimer, Tg 1, Tg 2, Tg} 3 ··· Tg n is the glass transition temperature of the homopolymer of each monomer (° C.). For the Tg of each homopolymer, for example, the numerical values described in the polymer handbook and the like can be used.

The component (A) is not limited except that it satisfies the above characteristics (a1) and (a2), and is preferably not limited except that the glass transition temperature is −70 to −50 ° C., and is arbitrary. Acrylic polymer can be used. Examples of the acrylic polymer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, pentyl (meth) acrylic acid, and (meth) acrylic acid. Hexyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, (meth) acrylic (Meta) acrylic acid ester monomers such as palmityl acid and stearyl (meth) acrylate; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, and β-carboxyethyl (meth) acrylate; (meth) acrylic acid. Epoxy group-containing monomers such as glycidyl and 4-hydroxybutyl (meth) acrylate glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, One or more of hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; Examples thereof include a polymer or a copolymer using a mixture of the above as a monomer. Note that (meth) acrylic acid means acrylic acid or methacrylic acid. (Meta) acrylate means acrylate or methacrylate. As the component (A), one kind or a mixture of two or more kinds of these can be used.

The component (B) is a compound having two or more isocyanate groups (-N = C = O) in one molecule. The above component (B) imparts an appropriate hardness to the pressure-sensitive adhesive and functions to prevent peeling, turning over, and the occurrence of mess.

Examples of the compound having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexylisocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, and triisholon diisocyanate. Polyisocyanates such as methylolpropane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and block-type isocyanate of the above polyisocyanate. Urethane cross-linking agents and the like can be mentioned. As the compound having two or more isocyanate groups in one molecule, one kind or a mixture of two or more kinds thereof can be used. Further, at the time of cross-linking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as needed.

The blending amount of the component (B) is usually 0 from the viewpoint of imparting an appropriate hardness to the pressure-sensitive adhesive with respect to 100 parts by mass of the component (A) and preventing peeling, turning, and generation of mess. It may be 1 part by mass or more, preferably 0.5 part by mass or more, and more preferably 1.0 part by mass or more. On the other hand, from the viewpoint of maintaining the adhesive strength at low temperature, it may be usually 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1.6 parts by mass or less.

In order to impart a predetermined color to the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention, a colorant is usually used. Further, a flame retardant or the like may be used for a normal purpose (flame retardant or nonflammable in the case of a flame retardant) and at the same time for the purpose of imparting a predetermined color.

The colorant is not particularly limited, and any colorant can be used. Examples of the above-mentioned colorants include organic colorants; CI Pigment Blue28, CI Pigment Blue36, CI Pigment Brown24, CI Pigment Yellow53, CI Pigment Green17, CI Pigment Green17, CI Pigment Black28, CI Pigment Black28, and CI Pig. Inorganic composite oxide-based colorants; titanium dioxide, red iron oxide (ferrous oxide), copper-chromium alloy, iron-chromium-tin-titanium alloy, nickel-antimon-titanium alloy, chromium-antimon-titanium alloy, and carbon Inorganic colorants such as black; etc. can be mentioned.

As the colorant, those having good dispersibility are preferable from the viewpoint of designability. In the present specification, the colorant having good dispersibility means that the 400 mesh pass fraction measured by the following method is usually 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more, still more preferably. It means a colorant of 99% by mass or more.

In the present specification, the 400 mesh pass fraction of the colorant is a value measured by the following method. It is possible to put 10 g of a colorant in a 1 liter beaker, pour 200 ml of methyl ethyl ketone, and use a stirrer (for example, a desktop stirrer "TK Homojitter f model (trade name)" manufactured by Tokushu Kagaku Kogyo Co., Ltd.). After stirring for 10 minutes at a stirring speed of 500 rpm, the methyl ethyl ketone suspension of the colorant was immediately filtered using a 400 mesh wire mesh. The 400 mesh pass fraction was calculated from the following equation.
(W _0- W ₁ ) / W ₀ x 100 (mass%)
Here, W ₀ is the amount of the colorant put into the beaker, and W ₁ is the amount of the colorant remaining on the wire mesh without passing through the wire mesh.

The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention may further contain an arbitrary component, if desired, as long as it does not contradict the object of the present invention. Examples of the optional component include a flame retardant, a photopolymerization initiator, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, a printability improver, an antioxidant, a weather resistance stabilizer, and the like. Additives such as light-resistant stabilizers, UV absorbers, heat stabilizers, and fillers can be mentioned. The blending amount of the optional component is not particularly limited, but may be about 0.01 to 100 parts by mass, with the component (A) as 100 parts by mass.

The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention can be obtained by mixing and stirring these components.

The peak top value of tan δ on the lowest temperature side of the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention is preferably −5 ° C. or lower, more preferably -5 ° C. or lower, from the viewpoint of improving the enforceability in the cold winter season. It may be -10 ° C or lower. On the other hand, from the viewpoint of maintaining the adhesive strength at a high temperature and preventing peeling, turning, and generation of mess, the temperature may be preferably −20 ° C. or higher, more preferably −15 ° C. or higher.

In the present specification, the peak top value of tan δ on the lowest temperature side of the pressure-sensitive adhesive is punched from a 1 mm thick sheet using the dynamic viscoelasticity measuring device “EXSTAR 6100DMS (trade name)” of Seiko Instruments Co., Ltd. A disk-shaped sample having a diameter of 5 mm and a thickness of 1 mm was attached to both sides of the tip of the shear chuck, set by a viscoelastic clamp base, held at a temperature of −45 ° C. for 10 minutes, and then heated at a temperature of 3 ° C. It is the peak top temperature of the peak appearing on the lowest temperature side in the temperature-tan δ curve obtained by raising the temperature to 100 ° C. under the condition of / min and frequency 0.1 Hz. Here, in the above 1 mm thick sheet, the pressure-sensitive adhesive is scraped from the pressure-sensitive adhesive film, and 150 parts by mass of a solvent (a 2: 1 (volume ratio) mixed solvent of ethyl acetate and butyl acetate) is used with respect to 100 parts by mass of the scraped pressure-sensitive adhesive. Is added and dissolved well, then poured into a flat mold so that the thickness after drying becomes 1 mm, allowed to stand, dried at room temperature (23 ° C.) for 24 hours, and further vacuum dried at a temperature of 30 ° C. for 8 hours. And created.

The method for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention using the above-mentioned pressure-sensitive adhesive is not particularly limited, and a known web coating method can be used. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. The pressure-sensitive adhesive layer may be formed directly on the pressure-sensitive adhesive layer-forming surface of the film base material, or may be formed on the easily-peelable surface of the release paper, and this may be formed on the pressure-sensitive adhesive layer-forming surface of the film base material. It may be transferred onto.

The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention (thickness in a portion other than the groove in the embodiment in which the air vent groove described later is provided) is not particularly limited, but is usually limited from the viewpoint of workability during construction. It may be 10 μm or more, preferably 30 μm or more, and more preferably 40 μm or more. On the other hand, it may be usually 75 μm or less, preferably 55 μm or less, and more preferably 50 μm or less, from the viewpoint of preventing appearance defects and the characteristic balance between the initial adhesive force in the embodiment in which the air vent groove is provided on the sticking surface.

The tackiness of the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention at a temperature of 5 ° C. is good from the viewpoint of improving the workability in the cold winter season, especially when it is constructed in the cold winter season, immediately after the construction. Despite the appearance, the problem that swelling occurs when the temperature inside the room rises after construction or when it receives sunlight from the window (hereinafter, it may be abbreviated as "problem of swelling over time during low temperature construction". From the viewpoint of suppressing or preventing), it may be preferably 12N or more, more preferably 13N or more, still more preferably 15N or more, and most preferably 17N or more. On the other hand, from the viewpoint of the balance between the enforceability in the cold winter season and the suppression of stickiness at the high temperature, it may be preferably 25 N or less, more preferably 23 N or less.

From the viewpoint of workability, the tackiness of the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention at a temperature of 35 ° C. may be preferably 12 N or more, more preferably 15 N or more. On the other hand, from the viewpoint of suppressing stickiness at high temperature, it may be preferably 23 N or less, more preferably 20 N or less.

In the present specification, the tackiness at a temperature of 5 ° C. is adjusted in an environment of a temperature of 5 ° C. and a relative humidity of 50% for 24 hours or more, and then under the same environment, a tackiness checker (model HTC-) manufactured by Toyo Seiki Seisakusho Co., Ltd. 1) is used, and the type of contact is a value measured under the conditions of a flat surface indenter (model AL-M1), a contact crimping force of 5 N, a crimping time of 3 seconds, and a number of repeated tests of 5 times. The tackiness at a temperature of 35 ° C. is a value measured in the same manner as the tackiness at a temperature of 5 ° C. under the same environment after adjusting the state for 24 hours or more in an environment of a temperature of 35 ° C. and a relative humidity of 50%. In the mode of providing the air vent groove described later, the measured value is used as it is without considering the existence of the groove.

It is preferable to provide an air vent groove on the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention (the surface to be adhered to a wall or the like). Poor appearance such as swelling and wrinkles that can be seen immediately after the enforcement can be prevented or suppressed by providing the above-mentioned air vent groove. The shape of the air vent groove and the method of providing the air vent groove are known, for example, described in JP-A-2006-0707273, JP-A-2002-544364, and International Publication No. 2005/10049. It may be a shape and a method.

2. Film substrate:
The film base material is a layer that serves as a base material for the pressure-sensitive adhesive film of the present invention.

Examples of the film base material include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylicimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Based resin: Cellulous resin such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene copolymer, styrene -Sterite resins such as ethylene / ethylene / propylene / styrene copolymers and styrene / ethylene / butadiene / styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluororesins such as vinylidene fluorides In addition, resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulphon, and polyethersulphon; can be mentioned. These films include non-stretched films, uniaxially stretched films, and biaxially stretched films. Further, it includes a laminated film in which two or more layers of one or more of these are laminated.

Among these, as the film base material, a polyvinyl chloride resin film is preferable from the viewpoint of imparting good workability in any of the cold winter season and the hot summer season.

Examples of the polyvinyl chloride resin used as the material of the polyvinyl chloride resin film include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride / vinyl acetate copolymer, and vinyl chloride / (meth) acrylic acid. Polymer, vinyl chloride / methyl (meth) acrylate copolymer, vinyl chloride / ethyl (meth) acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / Propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary copolymer, vinyl chloride / styrene / acrylonitrile Three-way copolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate ternary copolymer, vinyl chloride / acrylonitrile A vinyl chloride-based copolymer of vinyl chloride such as a copolymer, vinyl chloride or various vinyl ether copolymers and another monomer copolymerizable with vinyl chloride; polyvinyl chloride such as a post-chlorinated vinyl copolymer or chloride. A modified (chlorinated, etc.) vinyl-based copolymer; etc. can be mentioned. Further, a chlorinated polyolefin having a chemical structure similar to that of polyvinyl chloride, such as chlorinated polyethylene, may be used. As the polyvinyl chloride-based resin, one kind or a mixture of two or more kinds of these can be used.

The polyvinyl chloride-based resin may further contain other resins usually used in the polyvinyl chloride-based resin composition. The blending ratio of the other resin is not particularly limited as long as it does not contradict the object of the present invention, but is usually 0 to 40% by mass, preferably 0 to 0, assuming that the total of the above polyvinyl chloride resin and the other resin is 100% by mass. It may be 30% by mass, more preferably 5 to 25% by mass.

Examples of the other resins include ethylene / vinyl acetate copolymer; ethylene / (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer; ethylene / ethyl (meth) acrylate copolymer; Combined; methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, acrylonitrile / styrene / acrylic acid ester graft copolymer , Core-shell rubber such as methacrylic acid ester / acrylic acid ester rubber graft copolymer, methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymer; and the like. As the other resin, one kind or a mixture of two or more kinds of these can be used.

Further, the polyvinyl chloride-based resin may further contain a plasticizer usually used in the polyvinyl chloride-based resin composition. The blending amount of the plasticizer is usually 100 parts by mass or less, preferably 10 to 30 parts by mass, and more preferably 15 to 25 parts by mass, with the total of the polyvinyl chloride resin and the other resin as 100 parts by mass. May be.

Examples of the plasticizer include phthalic acid ester-based plasticizers, trimellitic acid ester-based plasticizers, pyromellitic acid ester-based plasticizers, adipic acid ester-based plasticizers, itaconic acid ester-based plasticizers, and citric acid ester-based plasticizers. Examples thereof include agents, cyclohexanedicarboxylate-based plasticizers, and epoxy-based plasticizers.

Examples of the plasticizer include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butanediol as polyhydric alcohols. Using 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., as polyvalent carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, pimeric acid , Oxalic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, etc. can.

Examples of the phthalate-based plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, and ditridecyl phthalate. Examples thereof include dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.

Examples of the trimellitic acid ester-based plasticizer include tri (2-ethylhexyl) trimellitate, tri (n-octyl) trimellitate, and tri (isononyl) trimellitate.

Examples of the adipic acid ester-based plasticizer include bis (2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.

Examples of the epoxidized plasticizer include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.

Other plasticizers include trimellitic acid-based plasticizers, tetrahydrophthalic acid diester-based plasticizers, glycerin ester-based plasticizers, epoxy hexahydrophthalic acid diester-based plasticizers, isosorbide diester-based plasticizers, and phosphate-based plasticizers. Agents, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, pyromellitic acid plasticizers, biphenyltetracarboxylic acid ester plasticizers, chlorine plasticizers, etc. I can give it.

As the plasticizer, one kind or a mixture of two or more kinds of these can be used.

Further, the polyvinyl chloride-based resin may further contain a substance usually used in the polyvinyl chloride-based resin composition as long as it does not contradict the object of the present invention. Optional ingredients that can be included include pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weathering stabilizers, heat stabilizers, nucleating agents, mold release agents, antistatic agents, urea-formaldehyde wax, and , Additives such as surfactants; and the like. The blending amount of these optional components is usually about 0.01 to 50 parts by mass when the total of the polyvinyl chloride resin and the other resin is 100 parts by mass.

The method for obtaining the polyvinyl chloride resin film using the polyvinyl chloride resin is not particularly limited. Examples of the above method include a method of using an apparatus equipped with a calendar roll rolling machine and a take-up machine, a method of using an apparatus equipped with an extruder, a T-die, and a take-up machine, and the like. ..

Examples of the calendar roll rolling machine include an upright type 3 roll, an upright type 4 roll, an L type 4 roll, an inverted L type 4 roll, and a Z type roll.

Examples of the extruder include a single-screw extruder, a co-rotating twin-screw extruder, and a different-direction rotating twin-screw extruder.

Examples of the T-die include a manifold die, a fishtail die, a coat hanger die, and the like.

The thickness of the polyvinyl chloride resin film is not particularly limited, but from the viewpoint of handleability, it may be usually 20 μm or more, preferably 50 μm or more, and more preferably 80 μm or more. On the other hand, from the viewpoint of workability at the time of construction, it may be usually 400 μm or less, preferably 300 μm or less, and more preferably 250 μm or less.

If desired, a printing layer may be provided on the front surface of the film base material in an actual use state in order to enhance the design feeling. The printing layer is provided to impart high designability, and can be formed by printing an arbitrary pattern with an arbitrary ink and an arbitrary printing machine.

Printing can be applied, either directly or through an anchor coat, on the front surface of the film substrate in actual use, either entirely or partially. The patterns include metallic patterns such as hairlines, wood grain patterns, stone grain patterns that imitate the surface of rocks such as marble, fabric patterns that imitate cloth texture and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, etc. And patchwork etc. can be mentioned. As the printing ink, a binder mixed with a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, and polyamides. Resins such as based resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins, and resin compositions thereof can be used. Further, in order to give a metallic design, aluminum, tin, titanium, indium, oxides thereof and the like are known wholly or partially on the front surface in the actual use state of the film base material. It may be vapor-deposited by the method of.

In order to protect the print layer, a protective coating film layer may be further provided on the surface of the print layer.

Examples of the coating material for forming the protective coating layer include coating materials containing urethane-based resin, polyester-based resin, acrylic-based resin, vinyl acetate-based resin, vinyl chloride-based resin, silicone-based resin, fluorine-based resin, and the like as main components. Can be given. Among these, paints containing urethane-based resin, polyester-based resin, and acrylic-based resin as the main components are preferable. As the coating material for forming the protective coating film layer, a coating material containing one or a mixture of two or more of these as a main component can be used.

The coating material for forming the protective coating film layer may contain 1-methoxy-2-propanol, ethyl acetate, n acetate, if desired.
Organic solvents such as butyl, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone can be used.

The coating material for forming the protective coating film layer includes, if desired, an antistatic agent, a surfactant, a leveling agent, a thixogenic agent, a stain inhibitor, a printability improver, an antioxidant, and a weather resistance stabilizer. , Light resistance stabilizer, ultraviolet absorber, heat stabilizer, colorant, filler and other additives may be contained in one type or two or more types.

The coating material for forming the protective coating film layer is obtained by mixing and stirring these components.

The method for forming the protective coating film using the coating film for forming the protective coating film layer is not particularly limited, and a known web coating method can be used. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating and die coating.

The thickness of the protective coating film layer is not particularly limited, but may be preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more from the viewpoint of the protective function. On the other hand, from the viewpoint of the handleability of the web and the workability at the time of forming the coating film, the thickness of the protective coating film layer may be preferably 100 μm or less, more preferably 50 μm or less.

When the coating film layer forms a front surface (a surface that is normally visible in the constructed state) in the actual use state of the adhesive film of the present invention, it becomes the front surface in the actual use state of the adhesive film. The L * a * b * coordinates measured with the surface as the measurement surface strongly reflect the colors of the printing layer and the film substrate that are usually observed through the coating film layer. In the present invention, this is used as it is as the L * a * b * coordinates of the front surface of the adhesive film in the actual use state. The same applies to any layer that forms the front surface in the actual use state of the pressure-sensitive adhesive film.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Measurement method (a) Meski (inconspicuousness of meski):
1. 1. Preparation of measurement sample:
In the following examples, from the laminate of the release paper and the adhesive layer obtained by using the adhesive (in the case of Example 1, the following (α-1)), the machine direction of the laminate is the length. Cut out a rectangular piece of 120 mm in length and 50 mm in width so that it faces the direction, and put the piece on the gypsum board "Tigerboard (trade name)" of Yoshino Gypsum Co., Ltd. and the rubber-based primer "Benridine" of Sangetsu Co., Ltd. "NEW RT (trade name)" was applied using a sponge roller, dried, and subjected to a primer treatment. Next, the pressure-sensitive adhesive layer of the small pieces was placed and pressed on the treated surface of the treated gypsum board so as to be on the treated gypsum board side, and the small pieces were attached to the treated gypsum board. Next, from the film base material (in the case of Example 1, the following (β-1)), a rectangular film having a length of 60 mm and a width of 50 mm so that the machine direction of the film base material is the length direction. Two pieces were cut out. Next, the release paper is removed from the small pieces bonded to the treated gypsum board, and the film pieces are placed on the surface of the adhesive layer of the small pieces with the short sides of the film pieces having a width of 1 mm. A measurement sample was obtained by pasting the film pieces so that the pressure-sensitive adhesive layer-forming surface of the film piece was on the pressure-sensitive adhesive layer side so as to face each other while providing a gap between the two. FIG. 2 shows a conceptual diagram of the measurement sample. Further, a comparative sample was prepared in the same manner except that the short sides of the film pieces were attached so as to face each other so as not to provide a gap at all.

2. Evaluation test:
In a test room with an illuminance of 50 lux, a person having a corrected visual acuity of 1.0 on the side used for the test visually observed the sample with one eye from a predetermined distance and evaluated whether or not the meshi could be visually observed. Here, "the meski can be visually recognized" means that the operation of visually observing the measurement sample or the comparison sample with one eye without informing the observer of which sample is repeated 5 times (at least once). Refers to the fact that the above-mentioned measurement sample is observed), and it means that it was possible to correctly answer which sample was observed five times. If there was an incorrect answer even once, it was judged that the meski could not be visually recognized.
◯: The measurement sample cannot be visually recognized even at a distance of 1.2 m.
Δ: The measurement sample can be visually recognized at a distance of 1.2 m. However, the measurement sample cannot be visually recognized at a distance of 3.5 m.
X: The measurement sample can be visually recognized even at a distance of 3.5 m.

(B) Tackiness at a temperature of 5 ° C:
After adjusting the condition for 24 hours or more in an environment with a temperature of 5 ° C and a relative humidity of 50%, a tackiness checker (model HTC-1) manufactured by Toyo Seiki Seisakusho Co., Ltd. is used in the same environment, and the type of contact is flat. The tackiness of the surface of the pressure-sensitive adhesive film on the pressure-sensitive adhesive layer side was measured under the conditions of a surface indenter (model AL-M1), a contact pressure bonding force of 5 N, a pressure bonding time of 3 seconds, and a number of repeated tests of 5 times. The results shown in the table are the average values of the five tests.

(C) Tackiness at a temperature of 35 ° C:
After adjusting the state for 24 hours or more in an environment of a temperature of 35 ° C. and a relative humidity of 50%, the same procedure as in the above test (b) was carried out in the same environment.

(D) Peak top temperature of tan δ on the lowest temperature side of the adhesive:
The pressure-sensitive adhesive is scraped from the pressure-sensitive adhesive film, and 150 parts by mass of a solvent (a 2: 1 (volume ratio) mixed solvent of ethyl acetate and butyl acetate) is added to 100 parts by mass of the scraped pressure-sensitive adhesive to dissolve it well. The sheet was poured into a flat mold so that the thickness after drying was 1 mm, allowed to stand, dried at room temperature (23 ° C.) for 24 hours, and further vacuum dried at a temperature of 30 ° C. for 8 hours to prepare a 1 mm thick sheet. .. Next, using the dynamic viscoelasticity measuring device "EXSTAR 6100DMS (trade name)" of Seiko Instruments Co., Ltd., a disk-shaped sample having a diameter of 5 mm and a thickness of 1 mm obtained by punching from the 1 mm thick sheet obtained above was prepared. Attach one to each side of the tip of the shear chuck, set it with a shear clamp base, hold it at a temperature of -45 ° C for 10 minutes, and then heat it at a temperature of 3 ° C / min and a frequency of 0.1 Hz at a temperature of 100 ° C. The peak top temperature of the peak appearing on the lowest temperature side in the temperature-tan δ curve obtained by raising the temperature to

(E) Low temperature workability (promotion test of swelling over time during low temperature work):
Apply Sangetsu Co., Ltd.'s rubber-based primer "Benridine NEW RT (trade name)" to Yoshino Gypsum Co., Ltd.'s 12.5 mm thick gypsum board "Tiger Board (trade name)" and dry it. Then, the base treatment was performed. Next, after adjusting the state of the treated gypsum board and the adhesive film obtained above in an environment of a temperature of 5 ° C. and a humidity of 50% for 24 hours or more, the adhesive film was applied to the base-treated surface of the treated gypsum board with a cutting edge. Using a squeegee having a width of 5 mm and a width of 10 cm, a load of 150 to 230 gf was applied to adhere and crimp. Subsequently, the surface of the treated gypsum board on which the adhesive film was adhered and crimped was subjected to a 1200 W household dryer, and the temperature of the entire surface of the adhesive film was 40 ° C. from a position 5 cm away from the adhesive film. It was blown and heated until it became. The surface of the adhesive film was visually observed and evaluated according to the following criteria.
Rank 6: No swelling Occurrence Rank 5: Swelling is slight. The area of the bulging portion is less than 5% of the total.
Rank 4: The occurrence of swelling is small. The area of the swelled portion is 5% or more and less than 15% of the whole.
Rank 3: There are not many swellings. The area of the swelled portion is 15% or more and less than 25% of the whole.
Rank 2: There are many swellings. The area of the swelled portion is 25% or more and less than 40% of the whole.
Rank 1: The occurrence of swelling is very high. The area of the bulging portion is 40% or more of the whole.

(F) Low temperature adhesive strength:
Except for the fact that the treated gypsum board obtained in the same manner as in the above test (e) was used as a test board, the treated surface was used as an adhesive film bonding surface, and the 90 ° peeling adhesive strength was measured under the condition of a temperature of 5 ° C. Measured according to 10 adhesive strength of JIS Z0237: 2009.

(G) Low temperature bending workability:
After adjusting the condition of the aluminum frame "Aluminum frame for brackets (trade name)" of Misumi Co., Ltd. and the adhesive film in an environment of temperature 5 ° C and humidity 50% for 24 hours or more, the adhesive film is 90 of the aluminum frame. ° The workability when adhesively and crimped to the bent portion (the curvature of the portion is 0.2R) using the above squeegee and fingers was evaluated according to the following criteria.
Rank 5: Can be easily and satisfactorily adhered and crimped.
Rank 4: Good adhesion and crimping.
Rank 3: Good adhesion and crimping can be achieved by squeezing sufficiently.
Rank 2: Even if it is squeezed sufficiently, some floating remains in and near the 90 ° bent part of the aluminum frame.
Rank 1: Even if it is sufficiently squeezed, floating remains in and near the 90 ° bent part of the aluminum frame.

Raw material used (α) Adhesive:
(Α-1) 100 parts by mass of the following component (A-1), 1 part by mass of the following component (B-1), 1.8 parts by mass of the following component (C-1), 10 parts by mass of the following component (D-1) A black pressure-sensitive adhesive obtained by mixing and stirring 3.4 parts by mass of the above component (D-2) and 23 parts by mass of the following component (D-3). The L *, a *, and b * coordinates are L * = 46.80, a * = -0.35, and b * = -0.77.
(Α-2) 100 parts by mass of the following component (A-1), 1 part by mass of the following component (B-1), 0.2 parts by mass of the following component (C-1), 10 parts by mass of the following component (D-1) A gray pressure-sensitive adhesive obtained by mixing and stirring 3.4 parts by mass of the above component (D-2) and 23 parts by mass of the following component (D-3). The L *, a *, and b * coordinates are L * = 56.01, a * = -0.70, and b * = -2.23.
(Α-3) 100 parts by mass of the following component (A-1), 1 part by mass of the following component (B-1), 0.2 parts by mass of the following component (C-1), 1.4 parts of the following component (C-2) Parts by mass, 0.2 parts by mass of the following component (C-3), 10 parts by mass of the following component (D-1), 3.4 parts by mass of the above component (D-2), and 23 parts by mass of the following component (D-3). A brown adhesive obtained by mixing and stirring the parts. The L *, a *, and b * coordinates are L * = 58.85, a * = 10.00, and b * = 13.00.
(Α-4) 100 parts by mass of the following component (A-1), 1 part by mass of the following component (B-1), 0.5 part by mass of the following component (C-4), 10 parts by mass of the following component (D-1) A white pressure-sensitive adhesive obtained by mixing and stirring 3.4 parts by mass of the above component (D-2) and 23 parts by mass of the following component (D-3). The L *, a *, and b * coordinates are L * = 94.45, a * = -0.03, and b * = 3.00.
(Α-5) 100 parts by mass of the following component (A-2), 1 part by mass of the following component (B-1), 1.8 parts by mass of the following component (C-1), 10 parts by mass of the following component (D-1) A black pressure-sensitive adhesive obtained by mixing and stirring 3.4 parts by mass of the above component (D-2) and 23 parts by mass of the following component (D-3). The L *, a *, and b * coordinates are L * = 46.71, a * = -0.34, and b * = -0.79.
(Α-6) 100 parts by mass of the following component (A-3), 1 part by mass of the following component (B-1), 1.8 parts by mass of the following component (C-1), 10 parts by mass of the following component (D-1) A black pressure-sensitive adhesive obtained by mixing and stirring 3.4 parts by mass of the above component (D-2) and 23 parts by mass of the following component (D-3). The L *, a *, and b * coordinates are L * = 46.92, a * = -0.31, and b * = -0.74.
(Α-7) 100 parts by mass of the following component (A-4), 1 part by mass of the following component (B-1), 1.8 parts by mass of the following component (C-1), 10 parts by mass of the following component (D-1) A black pressure-sensitive adhesive obtained by mixing and stirring 3.4 parts by mass of the above component (D-2) and 23 parts by mass of the following component (D-3). The L *, a *, and b * coordinates are L * = 46.59, a * = -0.33, and b * = -0.78.

The L *, a *, and b * coordinates of (α-1) above are obtained by placing a bar coater on one side of Toyobo Co., Ltd.'s 25 μm-thick biaxially stretched polyethylene terephthalate resin film “E5001 (trade name)”. The above (α-1) is applied to a thickness of 45 μm after drying, and dried to form an adhesive layer. The surface of the laminate obtained by forming the adhesive layer is used as a measurement surface, and JIS is used. According to Z8722: 2009, the spectrocolorimeter "CM600d (trade name)" of Konica Minolta Japan Co., Ltd. was used to measure the XYZ coordinates under the conditions including the geometric condition c and the component that becomes the mirror surface reflection, and this was L *. Calculated by converting to a * b * coordinates. The same applies to the above (α-2) to (α-7).

(A) Acrylic polymer:
(A-1) An acrylic polymer having an acid value of 23.3 mgKOH / g, a mass average molecular weight of 600,000, and a glass transition temperature of −58 ° C.
(A-2) An acrylic polymer having an acid value of 23.3 mgKOH / g, a mass average molecular weight of 800,000, and a glass transition temperature of −58 ° C.
(A-3) An acrylic polymer having an acid value of 26.8 mgKOH / g, a mass average molecular weight of 500,000, and a glass transition temperature of −53 ° C.
(A-4) An acrylic polymer having an acid value of 30.1 mgKOH / g, a mass average molecular weight of 450,000, and a glass transition temperature of −56 ° C.

(B) Trimethylolpropane adduct from Tosoh Co., Ltd. "Coronate L (trade name)".

(C) Colorant:
(C-1) The Copper / Chromium Alloy Colorant "BLACK30C965 (trade name)" manufactured by The Shepherd Color Company. 400 mesh pass fraction 99% by mass measured by the method described above.
(C-2) Iron / Chromium / Tin / Titanium Alloy Colorant "BROWN 30C888 (trade name)" from The Shepherd Color Company. 400 mesh pass fraction 99% by mass measured by the method described above.
(C-3) The Shepherd Color Company's nickel-antimony-titanium alloy-based colorant "YELLOW 30C119 (trade name)". 400 mesh pass fraction 99% by mass measured by the method described above.
(C-4) Titanium dioxide. 400 mesh pass fraction 96% by mass measured by the method described above.

(D) Optional component:
(D-1) Albemarle's brominated flame retardant "SAYTEX8010 (trade name)".
(D-2) Nihon Seiko Co., Ltd.'s diantimony trioxide "PATOX-M (trade name)".
(D-3) Methyl ethyl ketone.

(Β) Film substrate:
(Β-1) A black polyvinyl chloride resin film "TA8340 (trade name)" manufactured by RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 25.81, a * = −0.13, and b * = −1.09.
(Β-2) Dark brown polyvinyl chloride resin film "TA8314 (trade name)" of RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 32.97, a * = 3.55, and b * = 7.03.
(Β-3) Riken Technos Co., Ltd.'s dark brown-based polyvinyl chloride resin film with a grain pattern "TC8116 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 34.62, a * = 5.16, and b * = 6.86.
(Β-4) Riken Technos Co., Ltd.'s brown-based, grain-patterned polyvinyl chloride resin film "TC8224 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 48.11, a * = 14.57, and b * = 24.21.
(Β-5) Riken Technos Co., Ltd.'s gray-brown-based polyvinyl chloride-based resin film with a grain pattern "TC8115 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 50.15, a * = 5.92, and b * = 14.23.
(Β-6) Riken Technos Co., Ltd.'s brown-based, grain-patterned polyvinyl chloride-based resin film "TC8225 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 50.52, a * = 18.70, and b * = 25.52.
(Β-7) Riken Technos Co., Ltd.'s brown-based, grain-patterned polyvinyl chloride-based resin film "TC8223 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 54.00, a * = 17.77, and b * = 27.87.
(Β-8) A brown polyvinyl chloride resin film "TA8313 (trade name)" manufactured by RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 56.36 and a * = 4.63. b * = 10.23.
(Β-9) Riken Technos Co., Ltd.'s brown-based polyvinyl chloride resin film with a grain pattern "TC8114 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 58.72, a * = 8.06, and b * = 19.32.
(Β-10) Riken Technos Co., Ltd.'s brown-based, grain-patterned polyvinyl chloride-based resin film "TC8222 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 59.71, a * = 13.73, and b * = 24.60.
(Β-11) Riken Technos Co., Ltd.'s yellow-brown-based polyvinyl chloride-based resin film with a grain pattern "TC8221 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 61.56, a * = 17.93, and b * = 30.88.
(Β-12) Riken Technos Co., Ltd.'s yellow-brown-based polyvinyl chloride-based resin film with a grain pattern "TC8220 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 68.11, a * = 13.69, and b * = 30.29.
(Β-13) Riken Technos Co., Ltd.'s yellow-brown-based polyvinyl chloride-based resin film with a grain pattern "TC8219 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 78.32, a * = 6.35, and b * = 19.77.
(Β-14) Riken Technos Co., Ltd.'s ocher-colored polyvinyl chloride resin film "TA8336 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 83.01, a * = -0.25, and b * = 1.66.
(Β-15) Riken Technos Co., Ltd.'s gray-based polyvinyl chloride resin film "TC8113 (trade name)" with a grain pattern. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 83.77, a * = 1.70, and b * = 11.30.
(Β-16) Riken Technos Co., Ltd.'s gray-based, grain-patterned polyvinyl chloride-based resin film "TC8218 (trade name)". The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 83.94, a * = 1.45, and b * = 7.36.
(Β-17) A white polyvinyl chloride resin film "TC8332 (trade name)" manufactured by RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 96.28, a * = -1.07, and b * = 2.68.
(Β-18) A cream-colored polyvinyl chloride resin film "TA4753 (trade name)" manufactured by RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 92.81, a * = 0.67, and b * = 15.21.
(Β-19) Pink polyvinyl chloride resin film "TA4780 (trade name)" of RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 92.21, a * = 4.41, and b * = 0.23.
(Β-20) A bluish white polyvinyl chloride resin film "TA4771 (trade name)" manufactured by RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 92.48, a * = -4.69, and b * = -1.95.
(Β-21) A white polyvinyl chloride resin film "TA4762 (trade name)" produced by RIKEN TECHNOS CORPORATION. The L *, a *, and b * coordinates of the front surface in the actual use state are L * = 92.46, a * = -3.55, and b * = 7.68.

Among the above-mentioned film substrates, those having a handle (pattern) on the front surface in the actual use state (the above-mentioned (β-3) to (β-7), (β-9) to (β-13), Regarding (β-15) and (β-16)), a sample cut out to a size of 100 cm in the machine direction and 50 cm in the lateral direction was divided into 50 square measuring pieces having a side of 10 cm, and each measuring piece was absent. The L * a * b * coordinates at one location determined at random were measured, and the average value was calculated.

Example 1
Using a roll coater, the above-mentioned pressure-sensitive adhesive (α-1) was applied onto the peel-off surface of the release paper so that the thickness after drying was 45 μm, and dried in a drying oven to form a pressure-sensitive adhesive layer. The obtained laminate of the release paper and the pressure-sensitive adhesive layer was also used in the above test (a) Meski test. Subsequently, using the apparatus shown in the conceptual diagram in FIG. 3, the laminate 4 of the release paper and the pressure-sensitive adhesive layer obtained above and the polyvinyl chloride-based resin film (β-1) 5 were bonded to the laminate 4. The rotating metal laminate roll 6 preheated to a temperature of 30 ° C. so that the laminate 4 is on the metal laminate roll 6 side so that the agent layer is on the polyvinyl chloride resin film (β-1) 5 side. The pressure-sensitive adhesive film 8 was obtained by stacking and pressing the pressure-bonding roll 7 rotating with the above. The above test (a) was performed. The results are shown in Table 1.

Examples 2-17
The same procedure as in Example 1 was carried out except that the polyvinyl chloride resin film shown in Table 1 or Table 2 was used instead of the above (β-1). The results are shown in Table 1 or Table 2.

Examples 18-34
Except that the above (α-2) was used instead of the above (α-1) as the pressure-sensitive adhesive, and the polyvinyl chloride resin film shown in Table 2 or 3 was used instead of the above (β-1). The procedure was the same as in Example 1. The results are shown in Table 2 or Table 3.

Example 35-50
Except that the above (α-3) was used instead of the above (α-1) as the pressure-sensitive adhesive, and the one shown in Table 3 or Table 4 was used as the polyvinyl chloride resin film instead of the above (β-1). Was performed in the same manner as in Example 1. The results are shown in Table 3 or Table 4.

Example 51-71
Except that the above (α-4) was used instead of the above (α-1) as the pressure-sensitive adhesive, and the one shown in Table 4 or Table 5 was used as the polyvinyl chloride resin film instead of the above (β-1). Was performed in the same manner as in Example 1. The results are shown in Table 4 or Table 5.

Example 72
Examples other than using the above (α-3) instead of the above (α-1) as the pressure-sensitive adhesive and using the above (β-12) instead of the above (β-1) as the polyvinyl chloride resin film. An adhesive film was obtained in the same manner as in 1. The above tests (a) to (g) were performed. The results are shown in Table 6.

Example 73
Examples other than using the above (α-5) instead of the above (α-1) as the pressure-sensitive adhesive and using the above (β-8) instead of the above (β-1) as the polyvinyl chloride resin film. An adhesive film was obtained in the same manner as in 1. The above tests (a) to (g) were performed. The results are shown in Table 6.

Example 74
Examples other than using the above (α-6) instead of the above (α-1) as the pressure-sensitive adhesive and using the above (β-8) instead of the above (β-1) as the polyvinyl chloride resin film. An adhesive film was obtained in the same manner as in 1. The above tests (a) to (g) were performed. The results are shown in Table 6.

Example 75
Examples other than using the above (α-7) instead of the above (α-1) as the pressure-sensitive adhesive and using the above (β-8) instead of the above (β-1) as the polyvinyl chloride resin film. An adhesive film was obtained in the same manner as in 1. The above tests (a) to (g) were performed. The results are shown in Table 6.

In the adhesive film of the present invention, even if a mesh is generated, it is not noticeable. The preferable adhesive film of the present invention is excellent in adhesive strength, peeling resistance, curling resistance, and bending workability, and has good workability in any of the cold winter season and the hot summer season. However, even if mess is generated, it is not noticeable.

It is a graph created to consider the controlling factors of the inconspicuousness of Meski. It is a conceptual diagram of the sample of the Meski test. It is a conceptual diagram of the apparatus used for manufacturing an adhesive film in an Example.

1: Treatment surface of gypsum board 2: Adhesive 3: Surface that is the front surface in the actual use state of the adhesive film 4: Laminated body of release paper and adhesive layer 5: Polyvinyl chloride resin film 6: Metal laminate roll 7 : Crimping roll 8: Adhesive film

Claims (5)

A pressure-sensitive adhesive film having an adhesive layer on the one surface of the film substrate, the adhesive film for picture satisfying the following formula (1).
-26 ≤ (L1-L2) ≤ 4 ... (1)
Here, L1 is the brightness in the L * a * b * coordinates of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film.
L2 is the brightness at the L * a * b * coordinates of the front surface of the adhesive film in the actual use state.
The adhesive film for wallpaper according to claim 1, which satisfies the following formula (1-2).
-24 ≤ (L1-L2) ≤ 1 ... (1-2)
The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer contains a colorant.
The adhesive film for wallpaper according to claim 1 or 2, wherein the 400 mesh pass fraction of the colorant is 90% by mass or more.
The adhesive for forming the adhesive layer is
(A) 100 parts by mass of an acrylic polymer satisfying the following characteristics (a1) and (a2);
(B) Compound having two or more isocyanate groups in one molecule 0.1 to 3 parts by mass;
The adhesive film for wallpaper according to any one of claims 1 to 3.
(A1) The acid value is 18 to 27 mgKOH / g.
(A2) The mass average molecular weight is 500 to 1,000,000.
The adhesive film for wallpaper according to any one of claims 1 to 4, wherein the tackiness of the surface of the pressure-sensitive adhesive layer at a temperature of 5 ° C. is 12 to 25 N, and the tackiness at a temperature of 35 ° C. is 12 to 23 N.

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