JPH08302298A - Tacky film for marking - Google Patents

Abstract

PURPOSE: To prepare the subject film having effects such as excellent adhesivity between its layers and clear weatherability by laminating a pressure-sensitive tacky agent layer, a polyvinyl chloride film layer, a color printed layer and an ultraviolet ray-curing type clear covering layer of an acrylic urethane resin in turn. CONSTITUTION: (A) A pressure-sensitive tacky agent layer (e.g. natural rubber or an acrylic resin preferably having about 20-50μm thickness) is laminated with (B) a polyvinyl chloride layer (preferably having about 30-100μm thickness), (C) a color printed layer (preferably containing a vinyl chloride/vinyl acetate copolymer as a resin component) and (D) an ultraviolet ray-curing type clear covering layer of an acrylic urethane resin in turn to obtain the objective tacky film. The component D is formed by a composition containing (meth)acryloyl groups of more than about two in average in one molecule and a urethane acrylate oligomer having at least one urethane bonding in one molecule as essential components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel adhesive film for marking.

[0002]

BACKGROUND OF THE INVENTION Adhesive films for marking are, for example, affixed to a surface of an object such as a building, a vehicle, a machine, an electric appliance, a road sign, or a guard fence, which is cut into an arbitrary shape. It is used to decorate and display objects.

Conventionally, an adhesive film for marking is formed by forming a colored printing layer in a shape such as letters and figures on a polyvinyl chloride film, and then adding a polyisocyanate curing agent to a polyol resin thereon. An adhesive sheet coated with a urethane-based clear composition has been proposed (utility model registration publication No. 62-191845).

However, since the urethane clear composition used in the pressure sensitive adhesive sheet has a short pot life, it is added between the time when the curing agent is added to the polyol resin and the time when it is coated or printed. There is a drawback in that a stable finish appearance and performance of the coating film cannot be obtained due to the viscous property, and that once the viscosity and gelation are made, it takes time and effort to clean a coating machine, a printing machine and the like.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, as a clear layer, an acrylic urethane resin UV-curable clear
An adhesive film for marking formed by forming a coating layer,
The inventors have found that it solves all the conventional problems, and have completed the present invention.

That is, the present invention comprises a pressure-sensitive adhesive layer, a polyvinyl chloride film layer, a colored printing layer, and an acrylic urethane resin UV-curable clear-coating layer, which are laminated in this order for marking. Related to adhesive film.

The constituent features of the present invention will be described below.

The pressure-sensitive adhesive layer is, for example, a conventionally known pressure-sensitive adhesive such as natural rubber, acrylic resin, ethylene / vinyl acetate copolymer, polyurethane, polyester, silicone rubber, fluororubber, polyvinyl butyral and the like. It is a layer formed of the agent. The pressure-sensitive adhesive may contain, for example, a tackifier, a tackifier, an antiaging agent, a stabilizer, a colorant and the like. Also, one side of the pressure-sensitive adhesive layer (the side not the polyvinyl chloride film layer) is treated with a release agent such as silicon, wax or fluororesin, a release film such as a film or a film showing the release property itself. The sex sheet can be laminated. The thickness of the film is in the range of about 10-100 microns, preferably about 20-50 microns.

The polyvinyl chloride film layer is a colored or transparent flexible film that serves as a base material for the colored printing layer, facilitates the pressure bonding work, and enables display of innumerable designs by combining with the ink layer. To do.

The film is not particularly limited as long as it is usually used in the field, and a conventionally known film can be used. The film may also contain, for example, a plasticizer, a heat (light) stabilizer, a pigment and the like. The thickness of the film is in the range of about 20-500 microns, preferably about 30-100 microns.

The colored printing layer is made of, for example, polyamide resin,
By a colored printing composition prepared by blending a coloring agent and an organic solvent with a resin component such as chlorinated rubber, urethane resin, epoxy resin, acrylic resin, polyester resin, silicone resin, vinyl chloride, vinyl chloride / vinyl acetate copolymer, etc. It is formed. Of these, vinyl chloride / vinyl acetate copolymers have excellent solubility in organic solvents and have good adhesion to polyvinyl chloride films and acrylic urethane resin UV-curable clear-coating layers. Is preferred. The colored print layer is, for example,
It can be performed by printing means such as letterpress printing, intaglio printing, lithographic printing, and stencil printing (screen printing). Among these, the stencil printing method is preferable.

The acrylic urethane resin UV-curable clear coating layer comprises a urethane acrylate oligomer having an average of about 2 or more (meth) acryloyl groups in one molecule and at least one urethane bond in one molecule. It is formed by an acrylic urethane resin UV-curable clear composition containing as an essential component.

The urethane acrylate oligomer is, for example, a compound having a terminal hydroxyl group [eg (poly) ethylene glycol, (poly) propylene glycol, 1,
4-butylene glycol, 1,6-hexanediol,
Neopentyl glycol, etc.], polyester, polycaprolactone, polyether, etc., with a hydroxyl equivalent of about 2
It can be obtained by adding a double equivalent or more of polyisocyanate and reacting the hydroxyl group-containing acrylate monomer with the isocyanate group and the hydroxyl group while preventing the acrylic polymerization reaction.

Preferred examples of the polyisocyanate include hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate and pentamethylene diisocyanate. ,
Aliphatic polyisocyanate such as lysine diisocyanate
, Isophorone diisocyanate, alicyclic polyisocyanates such as 4-4'-methylenebis (cyclohexyl isocyanate), biuret type adducts of these polyisocyanates, and isocyanuric ring type adducts. And so on. Examples of the hydroxyl group-containing acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
Hydroxybutyl (meth) acrylate, (poly) alkylene glycol monoacrylate, and adducts of these monomers with lactones (eg, .epsilon.-caprolactone) are included.

The urethane acrylate oligomer has an average molecular weight of about 250 to 5,000, preferably about 500 to 30.
A range of 00 is preferred.

As an acrylic urethane resin UV-curable clear composition, in addition to the above-mentioned UV-curable components, other unsaturated monomers such as methyl (meth) acrylate, ethyl ( (Meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth)
C _1-24 alkyl or cycloalkyl ester of (meth) acrylic acid such as acrylate, unsaturated monomer containing carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Perfluorobutyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, perfluorooctyl (meth) acrylate, fluorine-containing unsaturated monomers such as ethylene trifluoride, styrene , Vinyltoluene, aromatic vinyl monomers such as benzoic acid, nitrogen-containing unsaturated monomers such as (meth) acrylonitrile, vinyl acetate, and the above hydroxyl group-containing acrylate monomers, vinyl alcohol, etc. Monomers containing one unsaturated group, and (poly) ethylene glycol di (meth) acrylate
, (Poly) propylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate
G, trimethylolpropane tri (meth) acrylate
G, tetramethyl methane tetra (meth) acrylate
Monomers containing two or more unsaturated groups in one molecule, such as G., can be used.

The mixing ratio of the above unsaturated monomers is
It is in the range of about 0 to 400 parts by weight, preferably about 20 to 100 parts by weight, per 100 parts by weight of the urethane acrylate oligomer.

Acrylic urethane resin UV-curable clear composition contains a UV-polymerization initiator. As the UV polymerization initiator, conventionally known ones can be used. Specifically, for example, 4-phenoxydichloroacetophenone, 4-ter-butyl-dichloroacetophenone, 4-ter-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-.
Methyl-1-phenylpropan-1-one, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)-
2-hydroxy-2-methylpropan-1-one, 4-
Acetophenones such as (2-hydroxyphenoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropane-1. Compounds, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4
-Thioxanthone compounds such as dimethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone, benzoin compounds such as benzoin and benzoin methyl ether, and dimethylbenzyl ketone.
And acylphosphine oxide. Among these, acetophenone compounds are preferable.

The mixing ratio of the above-mentioned ultraviolet polymerization initiator is
Usually, it is preferable to add about 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the urethane acrylate oligomer and the unsaturated monomers which can be added if necessary.

Further, a photopolymerization accelerator can be added in order to accelerate the photocrosslinking reaction by the above-mentioned ultraviolet polymerization initiator. Specifically, for example, triethylamine,
Examples include tertiary amines such as triethanolamine and 2-dimethylaminoethanol, alkylphosphines such as triphenylphosphine, and thiols such as β-thioglycol.

Acrylic urethane resin UV-curable clear compositions include UV absorbers (benzotriazol-based, benzophenone-based, anilide oxalate-based, cyanoacrylate-based, etc.), UV stabilizers (hinders) in addition to the above. Doamine, etc.), a cissing inhibitor, a fluidity modifier, an organic solvent and the like can be blended as necessary.

The acrylic urethane resin UV-curable clear composition is prepared by a conventionally known method, for example, a spray,
After coating and printing with a roll coater, a gravure coater, a screen or the like, a cured coating film can be formed by irradiating with ultraviolet rays. The thickness of the clear layer is preferably in the range of about 5 to 50 μm, preferably about 10 to 40 μm as a cured film thickness.

Examples of the ultraviolet ray irradiation source include a mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc, and a metal halide. The irradiation dose of ultraviolet rays is not particularly limited, but is usually 1
It is preferably in the range of 0 to 2000 mj / cm ² .

[0024]

EFFECT OF THE INVENTION The adhesive film for marking obtained by the present invention has a clear composition which is excellent in adhesion between layers, excellent in clear weather resistance, and capable of forming a clear film in a short time. Since there is no fear of thickening, the printing workability is excellent.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Examples.

Example 1 Releasable sheet, polyisobutyl acrylate adhesive (3
0 micron), and polyvinyl chloride sheet (white, 50
Micron) is used as the base material for the adhesive film
The surface of the polyvinyl chloride sheet of the substrate was screen-printed with VK911 Sumi [black, vinyl chloride / vinyl acetate copolymer manufactured by Teikoku Ink Co., Ltd.] to form a pattern, and then at room temperature for 2 hours. After left to dry, UV ink A
[Urethane diacrylate (polyester diol "phthalic anhydride / neopentyl glycol" 1 mol of hexamethylene diisocyanate was reacted with 2 mol of a terminal isocyanate group-containing polyester, 75 parts by weight of an average molecular weight of about 3000 oligomers obtained by reacting 2 mols of 2-hydroxyethyl acrylate per 1 mol of the polyester containing a terminal isocyanate group, 10 parts by weight of methyl methacrylate, 10 parts of butyl acrylate. Parts by weight, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholinopropane-1 acetophenone initiator 5
Parts by weight, and 4 parts by weight of a thioxanthone-based initiator of 2,4-dimethylthioxanthone are blended] and screen-printed to a film thickness of 10 microns to 500 mj / cm.
^The sheet of Example 1 was obtained by irradiating ultraviolet rays under the conditions of ² .

Example 2 In the same manner as in Example 1, except that the polyester diole of the urethane diacrylate of UV ink A was replaced with the polycaprolactone polyester diol, the average molecular weight was about 1. A sheet of Example 2 was obtained by the same procedure as in Example 1 except that 3500 of oligomer B was prepared and that this was replaced with oligomer A.

Comparative Example 1 Comparative Example 1 was prepared in the same manner as in Example 1 except that neopentyl glycol diacrylate was used in place of the urethane diacrylate of UV ink A.
Sheet was obtained.

The performance of the sheet is shown in Table 1.

[0030]

[Table 1]

In Table 1, the performance was evaluated according to the following criteria.

Appearance: The surface of the coating film was visually observed to evaluate the presence or absence of abnormalities such as a decrease in gloss, cracks and discoloration.

Adhesiveness: Cross-cut is applied to the coating film with a sharp knife so as to reach the polyvinyl chloride sheet from the clear coating film, and the adhesive cellophane tape is adhered to the coating film, and it is rapidly peeled off. After that, the surface condition was evaluated. ◯ indicates good, Δ indicates inferior, and x indicates extremely inferior.

Tensile elongation (%): Test conditions are test pieces
Length 150 mm x width 25 mm, pulling speed 300 mm / m
in, a measurement temperature of 25 ° C., and a tensilon type tensile tester.

Water resistance: It was immersed in tap water at 40 ° C. for 7 days, and the surface condition (blister, whitening, adhesion) was evaluated by comparing with the performance before the test. ◯ indicates good, Δ indicates inferior, and x indicates extremely inferior.

Acid resistance: 0.5 wt% of 0.1 wt% sulfuric acid water
After the solution was dropped and left at 40 ° C. for 4 hours, it was wiped with a cloth and the surface condition (blister, whitening, adhesion) was evaluated. ◯ indicates good, Δ indicates inferior, and x indicates extremely inferior.

Alkali resistance: A 0.1 wt% sodium hydroxide solution was added dropwise at 0.5 cc, left at 40 ° C. for 4 hours, and then wiped with a cloth to evaluate surface conditions (blister, whitening, adhesion). ◯ indicates good, Δ indicates inferior, and x indicates extremely inferior.

Accelerated weathering resistance: 10 using a sunshine weather ometer tester (Suga WE-SUN-HC type, black panel 63 ° C., 60 minutes irradiation, water injection for 12 minutes)
After conducting the 00 and 2000 hour tests, the surface state (gloss, discoloration, cracks, etc.) was examined for abnormalities in comparison with the coating film before the test.

[0039]

Claims (1)

[Claims] 1. A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer, a polyvinyl chloride film layer, a colored printing layer, and an acrylic urethane resin UV-curable clear coating layer, which are sequentially laminated.