JP2011012127A - Marking film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a marking film having not only elongation characteristics at room temperature and low temperatures and high tear strength but also good stickability and removability.SOLUTION: The marking film includes a film layer including an amino group-containing (meth)acrylic polymer and a carboxy group-containing (meth)acrylic polymer and a self-adhesive layer. The amino group-containing (meth)acrylic polymer is a polymer obtained by polymerizing a predetermined monomer and has a glass transition temperature of 0 to 80°C. The carboxy group-containing (meth)acrylic polymer is a polymer obtained by polymerizing a predetermined monomer and has a glass transition temperature of -10 to -60°C.

Description

  The present invention relates to a marking film.

In the fields of signboards, wall coverings, flooring materials, buildings, vehicles, etc., a marking film in which an adhesive layer is provided on a film substrate is used. In such a marking film, an acrylic resin having good weather resistance is used as a film substrate.
For example, Patent Document 1 discloses a film containing a carboxyl group-containing (meth) acrylic polymer and an amino group-containing (meth) acrylic polymer and having high tensile strength and elongation characteristics.
Patent Document 2 discloses a polymer blend of a carboxyl group-containing (meth) acrylic polymer and an amino group-containing (meth) acrylic polymer, wherein either or both of these polymers contain a hydroxyl group. A decorative film is disclosed that includes an acrylic film that includes the surface protective clear layer that is formed from a surface protective clear composition that includes an isocyanate-based crosslinking agent.

JP 2005-105256 A JP 2008-55690 A

  An object of this invention is to provide the marking film which has not only the elongation characteristic and high tear strength in room temperature and low temperature but favorable peeling off property.

That is, the present invention is a marking film comprising an amino group-containing (meth) acrylic polymer, a film layer containing a carboxyl group-containing (meth) acrylic polymer, and an adhesive layer,
The amino group-containing (meth) acrylic polymer is
(I) an amino group-containing (meth) acrylic monomer,
(Ii) a polymer having a glass transition temperature of 0 ° C. or more and 80 ° C. or less obtained by polymerizing a monomer containing methyl methacrylate or ethyl methacrylate and a (meth) acrylic ester monomer having a glass transition temperature lower than the components of (iii) and (ii) ,
The glass transition temperature obtained by polymerizing the carboxyl group-containing (meth) acrylic polymer with (iv) a carboxyl group-containing (meth) acrylic monomer and (v) a monomer containing methyl acrylate or ethyl acrylate is −10 ° C. or lower and −60 ° C. or higher. A marking film that is a polymer of the above is provided.

  The marking film of the present invention has excellent elongation characteristics at room temperature and low temperature, and has high tear strength and good peelability. Furthermore, since the marking film of the present invention contains a hydroxyl group-containing monomer, it does not lose its elongation property at room temperature and low temperature, and at the same time has a tear strength.

The marking film of the present invention comprises a film layer and an adhesive layer. Furthermore, a surface protective clear layer can be laminated on the surface of the film layer opposite to the pressure-sensitive adhesive layer.
The film layer has an amino group-containing (meth) acrylic polymer having a glass transition temperature (hereinafter sometimes referred to as “Tg”) of 0 ° C. or more and 80 ° C. or less, and a glass transition temperature of −10 ° C. or less −60 ° C. The polymer blend of the carboxyl group containing (meth) acrylic polymer which is the above is included.

Unless otherwise specified, the Tg of the polymer shown in the present specification indicates a value obtained from the FOX formula (the following formula) assuming that each polymer is copolymerized from n types of monomers.
1 / Tg = X1 / (Tg1 + 273.15) + X2 / (Tg2 + 273.15) +... + Xn / (Tgn + 273.15)
Tg1: Glass transition point of homopolymer of component 1 Tg2: Glass transition point of homopolymer of component 2 X1: Weight fraction of monomer of component 1 added during polymerization X2: Monomer of component 2 added during polymerization Weight fraction X1 + X2 +... + Xn = 1

The amino group-containing (meth) acrylic polymer of the present invention is
(I) an amino group-containing (meth) acrylic monomer,
(Ii) A polymer having a Tg of 0 ° C. or more and 80 ° C. or less obtained by polymerizing a monomer containing methyl methacrylate or ethyl methacrylate and a (meth) acrylic ester monomer having a glass transition temperature lower than that of the components (iii) and (ii). Furthermore, a hydroxyl group-containing monomer can be added as a constituent component.

  The (i) amino group-containing (meth) acrylic monomer is a monoethylenically unsaturated monomer having an amino group, such as dialkyl such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminoethyl methacrylate. Dialkylaminoalkyl (meth) acrylamide such as aminoalkyl (meth) acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-dimethylaminoethyl vinyl ether, N, N-diethylaminoethyl Dialkylaminoalkyl vinyl ethers such as vinyl ethers, and mixtures thereof.

  The (meth) acrylic ester monomer having a glass transition temperature lower than that of the component (ii) is a (meth) acrylic ester monomer having a Tg lower than that of methyl methacrylate or ethyl methacrylate. Since the Tg of methyl methacrylate is about 105 ° C. and the Tg of ethyl methacrylate is about 65 ° C., it is necessary to have a lower Tg.

  Examples of such monomers include butyl methacrylate (Tg about 20 ° C.), methyl acrylate (Tg about 8 ° C.), 2-ethylhexyl methacrylate (Tg about −10 ° C.), or lauryl methacrylate (Tg about −65 ° C.). be able to.

  Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates in which the alkyl group has 1 to 4 carbon atoms. Specific examples include hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, and hydroxybutyl acrylate. Among these, hydroxyethyl methacrylate or hydroxyethyl acrylate is preferable from the viewpoint of improving tearability at low temperatures.

  The content of the hydroxyl group-containing monomer in the amino group-containing polymer or carboxyl group-containing polymer can be about 0.1% by mass to about 5% by mass.

As a preferred composition of the amino group-containing (meth) acrylic polymer (Tg is 0 ° C. or higher and 80 ° C. or lower),
A combination of N, N-dimethylaminoethyl methacrylate, methyl methacrylate, and butyl methacrylate;
A combination of N, N-dimethylaminoethyl methacrylate, methyl methacrylate, and methyl acrylate, or a combination of these in addition of hydroxyethyl methacrylate or hydroxyethyl acrylate can be given.

The carboxyl group-containing (meth) acrylic polymer is
(Iv) A polymer having a Tg of −10 ° C. or lower and −60 ° C. or higher, obtained by polymerizing a carboxyl group-containing (meth) acrylic monomer and (v) a monomer containing methyl acrylate or ethyl acrylate. Furthermore, a hydroxyl group-containing monomer can be added as a constituent component.

  The (iv) carboxyl group-containing (meth) acrylic monomer is a monoethylenically unsaturated monomer having a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxypolycaprolactone monoacrylate, Mention may be made of monohydroxyethyl (meth) acrylate of phthalate, β-carboxyethyl acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and the like.

As a preferable composition of the carboxyl group-containing (meth) acrylic polymer (Tg is −10 ° C. or lower and −60 ° C. or higher),
A combination of acrylic acid and ethyl acrylate,
Mention may be made of a combination of acrylic acid, methyl acrylate and isooctyl acrylate, or a combination of these in addition of hydroxyethyl methacrylate or hydroxyethyl acrylate.

In any of the above combinations, other monomer components and additives can be added.
The content of methyl acrylate or ethyl acrylate in (v) in the carboxyl group-containing (meth) acrylic polymer can be 40% by mass to 99% by mass.
One method for obtaining the amino group-containing (meth) acrylic polymer is a method of copolymerizing a monoethylenically unsaturated monomer and an unsaturated monomer containing an amino group. Further, as one method for obtaining the carboxyl group-containing (meth) acrylic polymer, a method of copolymerizing a monoethylenically unsaturated monomer and an unsaturated monomer containing a carboxyl group can be mentioned.

  These copolymers can be performed by radical polymerization. In this case, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used. Initiators include organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, 2,2′-azobisisobutyronitrile, 2,2 ′. -Azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-methylpropionic acid) dimethyl, azobis-2,4-dimethylvaleronitrile (AVN), etc. An azo polymerization initiator is used. The usage-amount of an initiator shall be 0.05-5 mass parts normally per 100 mass parts of monomer mixtures.

  The weight average molecular weight of the polymer of the present invention can be selected in consideration of the balance of various performances of the film layer produced from the polymer. If the weight average molecular weight is too large, the viscosity of the polymer increases, making film production difficult. On the other hand, if the weight average molecular weight is too small, the tensile strength, elongation, weather resistance, etc. of the film are adversely affected.

  The amino group-containing (meth) acrylic polymer may have a weight average molecular weight of about 50,000 to about 1,000,000. Preferably, it can be about 50,000 to about 600,000. The carboxyl group-containing (meth) acrylic polymer may have a weight average molecular weight of about 200,000 to about 1,000,000.

The weight average molecular weight (Mw) of each polymer can be measured by GPC method (gel permeation chromatography). For example, the following conditions can be adopted as measurement conditions.
Apparatus: HP-1090 Series II (manufactured by Hewlett-Packard)
Solvent: Tetrahydrofuran Column: Plgel MIXED-Bx2 (300 mm, outer diameter 7.5 mm, inner diameter 5 mm)
Flow rate: 1.0 mL / min
Detection means: refractive index sample concentration: 0.1 wt%
Calibration standard: polystyrene

  The film layer of the present invention is prepared by mixing the amino group-containing (meth) acrylic polymer and the carboxyl group-containing (meth) acrylic polymer by a conventionally known method to obtain a polymer blend, and then by a normal film forming method. Can be produced. Specifically, for example, these polymer solutions are mixed, and if necessary, a volatile solvent such as toluene or ethyl acetate is added and applied onto the release surface of the release liner. A film can be produced by drying a volatile solvent. As this coating apparatus, a normal coater, for example, a bar coater, a knife coater, a roll coater, a die coater or the like can be used. This film can also be produced by a melt extrusion molding method.

  In production of the film layer, a film having desired tensile strength and elongation characteristics can be obtained by changing the blending ratio of each (meth) acrylic polymer. Specifically, the compounding ratio (mass ratio) of the amino group-containing (meth) acrylic polymer and the carboxyl group-containing (meth) acrylic polymer is 10:90 to 90:10, more preferably 20:80 to 90:10. , More preferably 30:70 to 90:10, and even more preferably 40:60 to 70:30.

  In the production of the film layer, a crosslinking agent may be added to the polymer blend. Examples of such cross-linking agents include bisamide-based cross-linking agents (for example, 1,1′-isophthaloyl-bis (2-methylaziridine)), aziridine-based cross-linking agents (for example, Nippon Shokubai Chemite PZ33, Avisia NeoCryl CX-100). , Carbodiimide crosslinking agents (for example, Nisshinbo Carbodilite V-03, V-05, V-07), epoxy crosslinking agents (for example, E-AX, E-5XM, E5C, manufactured by Soken Chemical), isocyanate crosslinking agents (for example, , Nippon Polyurethane Coronate L, Coronate HK, Bayer Death Module H, Death Module W, Death Module I) and the like can be used.

  The addition amount of the crosslinking agent can be about 0.01 to about 0.5 equivalents relative to the carboxyl group in the polymer containing a carboxyl group or the amino group in the polymer containing an amino group.

  In the film layer, conventionally known additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and a filler can be used as long as the effects of the present invention are not impaired. Among them, one or more kinds may be added.

  The thickness of the film layer is not particularly limited, and can be, for example, about 5 μm to about 300 μm, or about 30 μm to about 200 μm.

In the marking sheet of the present invention, a surface protective clear layer may be laminated on the surface of the film layer opposite to the pressure-sensitive adhesive.
The said surface protection clear layer contains an isocyanate type crosslinking agent with an isocyanate reaction resin component (for example, hydroxyl group containing compound), for example. The resin component preferably contains a highly transparent resin. Such a resin is, for example, a fluorine-based resin, a phthalate-based polyester (PET, PEN, etc.), an acrylic resin, a petroleum-resistant resin, or the like, and has an isocyanate-reactive functional group such as a hydroxyl group. The fluororesin is a polymer obtained by polymerizing a fluoromonomer. The fluorine-based monomer is, for example, a fluorine-based ethylene monomer such as vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, or trifluoroethylene chloride. In addition to fluorine-based monomers, one or more copolymerizable monomers such as methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, and acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate May be mixed. Moreover, you may use the resin composition which blended fluororesin and acrylic resin. For example, the acrylic polyol resin is crosslinked by causing hydroxyl groups in the polymer resin and hydroxyl groups in the (meth) acrylic polymer to react with an isocyanate-based crosslinking agent, thereby generating a urethane bond.

  Isocyanate-based crosslinking agents are polyisocyanates that react with hydroxyl groups and the like, for example, aromatic isocyanates such as isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, water. Examples thereof include aliphatic isocyanates such as added xylylene diisocyanate and hexamethylene diisocyanate, multimers of tolylene diisocyanate, and polyisocyanates such as coronate L and polymethylene polyisocyanate. The blending amount of the polyisocyanate is preferably such that the polyisocyanate and the hydroxyl group (NCO / OH) are 0.3 to 1.2. The hydroxyl group (OH) means a hydroxyl group (OH) in the isocyanate-reactive resin that forms the surface protective clear layer, and a part of the isocyanate group (NCO) is a hydroxyl group in the (meth) acrylic polymer. Used for reaction with (OH).

  The surface protective clear layer preferably has light transmittance as a whole. The light transmittance can be, for example, 60% or more, 70% or more, or 80% or more. The “light transmittance” in the present specification means a total light transmittance measured using a spectrophotometer or a color meter also having a photometer function and using light of 550 nm.

  The thickness of the surface protective clear layer can usually be 5 to 120 μm, or 10 to 100 μm.

  When the marking film of the present invention has a surface protective clear layer, it is preferable that one or both of the polymers constituting the film layer contain a hydroxyl group-containing monomer. In particular, when the surface protective clear layer contains an isocyanate-based cross-linking agent together with an isocyanate-reactive resin component (for example, a hydroxyl group-containing compound), the marking film can contribute to improvement in elongation at low temperature and tearability. Moreover, when the marking film of this invention has a surface protection clear layer, the film layer which has the target characteristic can be obtained even if it does not add a crosslinking agent to a polymer blend in the case of film layer preparation.

  The pressure-sensitive adhesive layer of the present invention comprises a conventionally known pressure-sensitive adhesive. Although it does not specifically limit as such an adhesive, For example, an acrylic adhesive, a polyester adhesive, a rubber adhesive, a silicone adhesive, or a polyurethane adhesive etc. can be mentioned.

  The pressure-sensitive adhesive layer is formed, for example, by preparing a pressure-sensitive adhesive layer with a liner having a pressure-sensitive adhesive layer formed on the release surface of the liner, and dry laminating the pressure-sensitive adhesive layer and the film layer. . Although the thickness of the said adhesive layer is not specifically limited, For example, it can be set as about 5 micrometers-about 200 micrometers.

  In the marking sheet of the present invention, a liner can be further laminated on the outer surface of the pressure-sensitive adhesive layer. Such a liner may be one generally used in the field such as an adhesive tape, and is not limited to a specific member. Suitable liners include, for example, paper, for example, plastic materials such as polyethylene, polypropylene, polyester, or cellulose acetate, or paper or other materials coated or laminated with such plastic materials. it can. These liners may be used as they are, but they can be used after being treated with a silicone treatment or other methods to improve the release characteristics.

  The marking film of the present invention can be produced by a conventionally known method, and is not limited. For example, it can be produced by laminating the film layer and the pressure-sensitive adhesive layer obtained above by dry lamination. In addition, in the case of further having a surface protective clear layer, a resin solution constituting the surface protective clear layer is prepared in advance, and this solution is applied to the surface of the film layer of the laminate of the film layer and the adhesive layer and dried. Can be produced.

  The thickness of the marking film of the present invention is not particularly limited, and can be, for example, about 30 μm to about 500 μm, or about 50 μm to about 300 μm.

  The marking film in the present invention preferably has a tear strength of 40 N / mm or more as measured by JISK7128-3 (1998) at room temperature (20 ° C.). When applying the marking film to the adherend, it is peeled off from the adherend for alignment. At this time, if the tear strength is 40 N / mm or more, the marking film is not torn. Can be peeled off.

  The marking film of the present invention can be used by being attached to a signboard, wall covering, flooring, building, vehicle or the like.

In the present specification, the following abbreviations may be used.
MA: methyl acrylate EA: ethyl acrylate MMA: methyl methacrylate BA: butyl acrylate BMA: butyl methacrylate
iBMA: isobutyl methacrylate IOA: isooctyl acrylate DM: dimethylaminoethyl methacrylate AA: acrylic acid HEMA: hydroxyethyl methacrylate HEA: hydroxyethyl acrylate 2MEA: 2-methoxyethyl acrylate EtAC: ethyl acetate MIBK: methyl isobutyl ketone In the book, “(meth) acryl” means acrylic or methacrylic.

The composition of the polymer, pigment, and crosslinking agent used in the examples are shown in Table 1. H1 to H8 represent amino group-containing (meth) acrylic polymers (amino group-containing polymers), and S1 to S17 represent carboxyl group-containing (meth) acrylic polymers (carboxyl group-containing polymers). In Examples 1 to 14 and Comparative Examples 1 to 7, the composition, addition amount, and crosslinking agent addition amount of the amino group-containing polymer and the carboxyl group-containing polymer were set to the values shown in Table 2.
Example 1
100 parts by mass of H1, 100 parts by mass of S1, and 0.2 parts by mass (solid content ratio) of the crosslinking agent 2 were added to 100 parts by mass of H1. The compatibility between the polymers was good. The composition was applied to a 50 μm release-treated polyester film (manufactured by Teijin DuPont Films) by knife coating, dried and crosslinked at 95 ° C. for 3 minutes and 155 ° C. for 2 minutes to obtain a film layer having a thickness of 50 μm. 0.2 parts by mass (solid content ratio) of the crosslinking agent 1 was added to 100 parts by mass of the adhesive polymer 1. The pressure-sensitive adhesive composition was applied onto a paper-based double-sided polyethylene laminate release paper by knife coating so that the thickness after drying was 30 μm, heated at 90 ° C. for 5 minutes, dried and crosslinked to obtain a pressure-sensitive adhesive layer. The film layer was dry laminated to obtain a sample.
Example 2
A sample was prepared in the same manner as in Example 1 except that the amount of S1 added was changed to 90 parts by mass.
Example 3
A sample was prepared in the same manner as in Example 1 except that the amount of S1 added was changed to 80 parts by mass.
Example 4
A sample was prepared in the same manner as in Example 1 except that the amount of S1 added was changed to 70 parts by mass.
Example 5
A sample was prepared in the same manner as in Example 1 except that the amount of S1 added was changed to 60 parts by mass.

Example 6
40 parts by mass of MIBK was added to 10 parts by mass of H1 and 50 parts by mass of Pigment 1, and stirred for 10 minutes with a mixer (ARE250 manufactured by Sinky Corporation) to obtain a pigment premix solution. A white film composition solution was prepared by mixing the pigment premix so that H1 was 100 parts by mass, Pigment 1 was 50 parts by mass, and S1 was 100 parts by mass. 0.2 parts by mass (solid content ratio) of the crosslinking agent 2 was added to 100 parts by mass of S1. The compatibility of polymer and pigment was good and easily dispersed. The composition was applied to a 50 μm release-treated polyester film (manufactured by Teijin DuPont Films) by knife coating, dried and crosslinked at 95 ° C. for 3 minutes and 155 ° C. for 2 minutes to obtain a film layer having a thickness of 50 μm. A film sample was obtained by dry lamination with the same pressure-sensitive adhesive as in Example 1.
Example 7
A sample was prepared in the same manner as in Example 4 except that S2 was changed and the crosslinking agent 2 was not added.
Example 8
A sample was prepared in the same manner as in Example 4 except that the process was changed to S3.
Example 9
A sample was prepared in the same manner as in Example 4 except that the process was changed to S4.

Example 10
A sample was prepared in the same manner as in Example 4 except that the process was changed to S5.
Example 11
A sample was prepared in the same manner as in Example 7 except that the amount of addition of S5 was changed to 110 parts by mass except that the amount was changed to S5.
Example 12
A sample was prepared in the same manner as in Example 11 except that the amount of S5 added was changed to 100 parts by mass.
Example 13
A sample was prepared in the same manner as in Example 11 except that the amount was changed to H3 and S8, and the addition amount of S8 was changed to 90 parts by mass.
Example 14
A sample was prepared in the same manner as in Example 13 except for changing to H4.

Comparative Example 1
A sample was prepared in the same manner as in Example 12 except that S6 was changed.
Comparative Example 2
A sample was prepared in the same manner as in Example 4 except that the addition amount of the crosslinking agent 2 was changed to 3 parts by mass in S7.
Comparative Example 3
A sample was prepared in the same manner as in Comparative Example 1 except that the amount of S6 added to H2 was changed to 100 parts by mass.
Comparative Example 4
A sample was prepared in the same manner as in Comparative Example 2 except that the crosslinking agent 2 was not added to H2.
Comparative Example 5
A sample was prepared in the same manner as in Example 4 except that the process was changed to S9.

Comparative Example 6
A sample was prepared in the same manner as in Example 4 except that the process was changed to S10.
Comparative Example 7
A sample was prepared in the same manner as in Comparative Example 4 except that the amount of S2 added was changed to 82 parts by mass in S2.

Example 15
60 parts by mass of S11 is prepared with respect to 100 parts by mass of H5 in terms of solid content, 30 parts by mass of butyl acetate (BuOAc) is added, and the mixture is stirred for 5 minutes with a mixer (ARE250 manufactured by Sinky Corporation) to prepare an acrylic composition solution. did. Next, the composition solution was applied to a 50 μm release-treated polyester film (manufactured by Teijin DuPont Films) by knife coating, and dried at 150 ° C. for 5 minutes to obtain a film layer having a thickness of 60 μm. Next, an acrylic pressure-sensitive adhesive solution having a composition ratio of 70: 22.5: 7.5 (mass ratio) with resistance to isooctyl acrylate / methyl acrylate / acrylic acid copolymer was prepared. The solvent was ethyl acetate, polymerization average molecular weight 360,000, Tg = −35 ° C. Prepare a pressure-sensitive adhesive solution of acrylic pressure-sensitive adhesive / crosslinking agent 1 = 100: 0.21 (solid content ratio) so that the thickness after drying on a paper-based double-sided polyethylene laminate release paper is 30 μm by knife coating. It was applied, dried at 90 ° C. for 5 minutes and cross-linked to form an adhesive layer. The obtained adhesive layer and the film layer were laminated by an adhesive and dry lamination. Furthermore, an acrylic polyol resin (Desmophen A365 made by Sumitomo Bayer Urethane) and polyhexamethylene diisocyanate (Sumidu N3300 made by Sumitomo Bayer Urethane) are mixed so that the NCO / OH equivalent ratio = 1.0, and the surface protective clear layer resin A solution was obtained. The polyester film is removed from the film layer of the laminate of the film layer and the pressure-sensitive adhesive layer obtained above, and the resin solution is applied to the removed surface by knife coating, followed by drying and crosslinking at 85 ° C. for 1.5 hours. Thus, a sample having a transparent protective layer film having a thickness of 3 μm was obtained.

Examples 16-26
A sample was prepared in the same manner as in Example 15 except that the composition and addition amount of the amino group-containing polymer and carboxyl group-containing polymer were set to the values shown in Table 3.
Example 27
60 parts by mass of S11 is prepared for 100 parts by mass of H5 in terms of solid content, 30 parts by mass of butyl acetate (BuOAc) is added, 80 parts by mass of pigment 1 is added, and 5 minutes with a mixer (ARE250 manufactured by Sinky Corporation). Stir to prepare a composition solution. Next, the composition solution was applied to a 50 μm release-treated polyester film by knife coating, and dried at 150 ° C. for 5 minutes to obtain a film having a thickness of 60 μm. Thereafter, samples were obtained in the same manner as in Example 15.
Example 28
An adhesive film sample was obtained in the same manner as in Example 27 except that the pigment was changed to Pigment 2 and the addition amount was changed to 1.6 parts by mass.

Comparative Examples 8-16
A sample was prepared in the same manner as in Example 15 except that the composition and addition amount of the amino group-containing polymer and carboxyl group-containing polymer were set to the values shown in Table 3.
Comparative Example 17
A sample was prepared in the same manner as in Example 15 except that the crosslinking agent 3 was added, and the composition and addition amount of the amino group-containing polymer and carboxyl group-containing polymer were set to the values shown in Table 3. The blending amount of the crosslinking agent was polymer: crosslinking agent 3 = 100: 6.7 (solid content ratio).
Comparative Example 18
A sample was prepared in the same manner as in Example 15 except that the crosslinking agent 1 was added and the composition and addition amount of the amino group-containing polymer and carboxyl group-containing polymer were set to the values shown in Table 3. The blending amount of the crosslinking agent was polymer: crosslinking agent 1 = 100: 6.8 (solid content ratio).
Comparative Example 19
A sample was prepared in the same manner as in Example 15 except that the crosslinking agent 4 was added and the composition and addition amount of the amino group-containing polymer and carboxyl group-containing polymer were set to the values shown in Table 3. The blending amount of the crosslinking agent was polymer: crosslinking agent 4 = 100: 19.2 (solid content ratio).
Comparative Example 20
A sample was obtained in the same manner as in Example 15 except that the surface protective clear layer was not provided.

Measurement of tearability The samples prepared in Examples and Comparative Examples were measured. The tear test piece was a right angle JIS K7128-3 (1998) non-cut angle type. The pulling speed was 200 mm / min, and N = 5. The results are shown in Tables 4 and 5.
Measurement of peelability The samples of Examples 1 to 14 and Comparative Examples 1 to 7 were measured. A film sample was cut into a length of 150 mm and a width of 70 mm to obtain a test piece. The test piece was affixed with a squeegee on a melamine baked coated plate manufactured by Partec under an environment of 23 ° C. Immediately after pasting, the film was peeled off at high speed, and the peel force was evaluated by sensory evaluation. When the film could be peeled without being broken, it was judged as “Good”, and when the film was broken at the time of peeling, it was judged as “Poor”. The results are shown in Table 4.
Measurement of Yield Strength Samples of Examples 1 to 14 and Comparative Examples 1 to 7 were cut to a length of 150 mm and a width of 25 mm, and a tensile rate of 100 mm and a pulling speed of 300 mm / min using Tensilon in an environment of 20 ° C. Yield strength (yield point) was measured. The results are shown in Table 4.
Measurement of elongation rate It measured based on the method prescribed | regulated to JISK7127 (1989). The shape of the test piece was measured with No. 1 type (width 25 mm), a tensile speed of 300 mm / min, and Tensilon RTF manufactured by AND. For samples prepared in all Examples and Comparative Examples, the elongation at a measurement temperature of 20 ° C. was measured. About the sample created in Examples 15-28 and Comparative Examples 8-20, the elongation rate in the measurement temperature of 5 degreeC was measured. The results are shown in Table 5.

Claims (8)

A marking film comprising an amino group-containing (meth) acrylic polymer, a film layer containing a carboxyl group-containing (meth) acrylic polymer, and an adhesive layer,
The amino group-containing (meth) acrylic polymer is
(I) an amino group-containing (meth) acrylic monomer,
(Ii) a polymer having a glass transition temperature of 0 ° C. or more and 80 ° C. or less obtained by polymerizing a monomer containing methyl methacrylate or ethyl methacrylate and a (meth) acrylic ester monomer having a glass transition temperature lower than the components of (iii) and (ii) ,
The glass transition temperature obtained by polymerizing the carboxyl group-containing (meth) acrylic polymer with (iv) a carboxyl group-containing (meth) acrylic monomer and (v) a monomer containing methyl acrylate or ethyl acrylate is −10 ° C. or lower and −60 ° C. or higher. Marking film that is a polymer.   The marking film according to claim 1, wherein at least one of the amino group-containing (meth) acrylic polymer and the carboxyl group-containing (meth) acrylic polymer is a polymer obtained by adding a hydroxyl group-containing monomer.   The marking film according to claim 1 or 2, wherein the (meth) acrylic ester monomer having a glass transition temperature lower than that of the component (ii) is selected from butyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate.   The marking film according to claim 2 or 3, wherein the hydroxyl group-containing monomer is a hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms.   The marking film according to claim 3 or 4, wherein the hydroxyl group-containing monomer is hydroxyethyl methacrylate or hydroxyethyl acrylate.   The marking film as described in any one of Claims 1-5 which laminated | stacked the surface protective layer on the surface on the opposite side to the adhesive layer of the said film layer.   The marking film according to claim 6, wherein the surface protective layer contains an isocyanate-reactive resin component and an isocyanate-based crosslinking agent.   The marking film according to any one of claims 1 to 7, wherein the tear strength at 20 ° C measured by JISK7128-3 (1998) is 40 N / mm or more.