JP5844010B2 - PRINTING COATING AGENT AND METHOD FOR PRODUCING PRINTING COAT FILM - Google Patents

Description

The present invention relates to a printing coating agent and a printing coating film, and more particularly to a printing coating agent and a printing film using a specific metal-based crosslinking accelerator.

  Conventionally, when printing on various film substrates, organic coating agents are mainly used to improve the adhesion of ink to the film substrate. A cross-linking agent is added to an organic coating agent in order to improve the durability of the coating film or impart performance, but a cross-linking accelerator should be added depending on the reactivity of the cross-linking agent. Has been done.

Conventionally, tin-based compounds having a butyl group such as tributyltin laurylate and dibutyltin dilaurate have been used as reaction accelerators for urethanization reactions, but there are concerns that these compounds may adversely affect the human body. There is a movement to limit its use, which is not preferable in terms of environmental problems. Although there is a coating agent that does not contain a metal compound as a reaction accelerator (see Patent Document 1), the reaction may be insufficient depending on the type of the crosslinking agent.

JP 2007-021862 A

  The present invention has been made in view of the above-described prior art, the film base material and the coating agent layer have excellent adhesion, and the printing ink has excellent adhesion and blocking resistance. It aims at providing the coating agent for printing which can form a coating agent layer, and the coating film for printing manufactured using it.

In order to solve the above problems, the present inventors have developed a specific metal-based cross-linking accelerator as a cross-linking accelerator in a coating agent for printing containing a polyester-based resin as a resin component and an isocyanate-based compound as a cross-linking agent. It has been found that the above problems can be solved by containing an agent, and the present invention has been completed based on this finding.

That is, the present invention relates to a polyester resin having a glass transition temperature of 40 to 105 ° C., a polyester resin having a glass transition temperature lower by 20 ° C. or more than the glass transition temperature of the polyester resin, and an isocyanate type as a crosslinking agent. Compound, and at least one metal-based crosslinking accelerator selected from bismuth-based crosslinking accelerator, titanium-based crosslinking accelerator, vanadium-based crosslinking accelerator, zirconium-based crosslinking accelerator, aluminum-based crosslinking accelerator, and nickel-based crosslinking accelerator The present invention provides a coating agent for printing characterized by containing an agent.
Further, the present invention provides the printing coating agent, wherein the mixing ratio of the polyester resin having a glass transition temperature lower by 20 ° C. or more is 1 to 50% by mass with respect to the total mass of all the polyester resins. A coating agent is provided.

Moreover, this invention provides the coating agent for printing whose said isocyanate type compound is hexamethylene diisocyanate in the said coating agent for printing.

Moreover, this invention provides the coating agent for printing whose said polyester-type resin is urethane-modified polyester-type resin in the said coating agent for printing.

Further, the present invention is to provide a method for producing a coated printing film characterized in that a coated printing agent described above, Ru provided for printing coating agent layer applied to the surface of the film substrate .

Further, the present invention provides the above method for producing a coated printing film, in which the film substrate is to provide a manufacturing method of polyethylene terephthalate resin, coated printing film is a film substrate made of a polypropylene resin or polyethylene resin is there.
Further, the present invention provides the above method for producing a coated printing film, there is provided a method for producing a coated printing film adhesive layer is provided on the back surface of the film substrate.

The coating agent for printing of the present invention can form a coating agent layer in which the film base material and the coating agent layer have excellent adhesion, and the printing ink has excellent adhesion and blocking resistance. . A method of manufacturing a coated printing film of the present invention has excellent adhesion and film substrate and the coating agent layer, and the adhesion of the printing ink, and printing coat is excellent in blocking resistance A film can be produced .

The printing coating agent of the present invention is a printing coating agent containing a polyester resin as a resin component.
Examples of polyester resins include polyester resins and urethane-modified polyester resins.
The polyester resin is preferably a polyester copolymer resin obtained by copolymerizing a dicarboxylic acid and a glycol compound.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, sulfoterephthalic acid, and 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as oxalic acid, sebacic acid, succinic acid, and adipic acid. Acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids Is preferably used.

Examples of the glycol compound include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylene glycol, triethylene glycol and the like are preferably used.

Examples of the urethane-modified polyester resin include those having a urethane bond in the polyester resin.
The urethane-modified polyester resin can be obtained, for example, by reacting a polyester resin having two or more functional groups such as a hydroxyl group in one molecule with a polyisocyanate compound.

As a polyisocyanate compound, the thing similar to the polyisocyanate compound as a crosslinking agent mentioned later can be used. The polyisocyanate compound used for urethane modification of the polyester resin can be used alone or in combination of two or more.

The polyester resin is preferably a urethane-modified polyester resin, and particularly preferably a urethane-modified polyester resin having a basic structure of an aromatic polyester. The basic structure of the aromatic polyester is one having a repeating unit derived from an aromatic compound in the main-chain polyester structure. For example, one or both of a dicarboxylic acid and a glycol compound which are part or all of a copolymer raw material Is obtained when is an aromatic compound.
Polyester resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The number average molecular weight of the polyester resin is preferably 5,000 to 100,000, more preferably 10,000 to 60,000.
The hydroxyl value of the polyester resin is preferably 1 to 50 mgKOH / g, more preferably 1 to 25 mgKOH / g, and even more preferably 1.5 to 20 mgKOH / g.

The acid value of the polyester resin is preferably 0 to 40 mgKOH / g, and more preferably 0 to 30 mgKOH / g.
The glass transition temperature of the polyester-based resin is preferably 40 to 105 ° C, more preferably 50 to 100 ° C, and further preferably 70 to 95 ° C.
When the number average molecular weight, the hydroxyl value, the acid value, and the glass transition temperature of the polyester resin are within the preferable ranges, the effects of the present invention can be further exhibited.

Moreover, in order to make the adhesion improvement of the coating agent layer to a film base material and printing ink and prevention of blocking compatible, the polyester-type resin which has a glass transition temperature lower by 20 degreeC or more than the glass transition temperature of the said polyester-type resin is used. The glass transition temperature is preferably −30 to 15 ° C., more preferably −25 to 5 ° C. As the glass transition temperature falls within the above preferable range and the more preferable range, the effect of improving the adhesion of the coating agent layer and preventing blocking can be further exhibited.

Examples of the polyester resin for improving the adhesion of the coating agent layer and preventing blocking include a polyester resin and a urethane-modified polyester resin as in the case of the polyester resin. The polyester resin for improving the adhesion of the coating agent layer and preventing blocking is preferably a polyester copolymer resin obtained by copolymerizing a dicarboxylic acid and a glycol compound. Specific examples of the dicarboxylic acid and the glycol compound include the same ones as described above.

Examples of the urethane-modified polyester resin include those having a urethane bond in the polyester resin.
The urethane-modified polyester resin can be obtained, for example, by reacting a polyester resin having two or more functional groups such as a hydroxyl group in one molecule with a polyisocyanate compound.

As the polyisocyanate compound, the same compounds as described above can be used. The polyisocyanate compound used for urethane modification of the polyester resin can be used alone or in combination of two or more.
The polyester resin for improving the adhesion of the coating agent layer and preventing blocking may be used singly or in combination of two or more.

Moreover, when using together the said polyester-type resin and the polyester-type resin for the adhesive improvement of a coating agent layer, and blocking prevention, it is preferable that both are the same kind polyester resins. For example, when the former polyester-based resin is a urethane-modified polyester resin, the latter is also preferably a urethane-modified polyester resin for improving adhesion and blocking of the coating agent layer used in combination with the latter, When the former polyester-based resin is a urethane-modified polyester resin having a basic structure of an aromatic polyester, the latter polyester resin for improving adhesion and preventing blocking of the coating agent layer used in combination is also the basic structure of an aromatic polyester. It is preferable that it is a urethane-modified polyester resin having.

As the number average molecular weight, the hydroxyl value, and the acid value of the polyester resin for preventing and blocking the coating agent layer become the following preferable range, more preferable range, and further preferable range, the adhesion improvement of the coating agent layer and The effect of preventing blocking can be further exhibited.

The number average molecular weight is preferably 5,000 to 100,000, more preferably 10,000 to 60,000.
The hydroxyl value is preferably 1 to 50 mgKOH / g, more preferably 1 to 15 mgKOH / g, and even more preferably 1.5 to 10 mgKOH / g.
The acid value is preferably 0 to 20 mgKOH / g, more preferably 0 to 8 mgKOH / g, and still more preferably 0 to 3 mgKOH / g.

The mixing ratio of the polyester resin for improving the adhesion of the coating agent layer and preventing blocking is preferably 1 to 50% by mass, more preferably 10 to 45% by mass with respect to the total mass of all polyester resins. 40% by mass is particularly preferred.
The printing coating agent of the present invention contains an isocyanate compound as a crosslinking agent together with the polyester resin.

As the isocyanate compound as a crosslinking agent, various isocyanate compounds can be used as long as they react with a functional group such as a hydroxyl group of the polyester resin to form a crosslinked structure.
The isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups per molecule.

Examples of the polyisocyanate compound include diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, pentaisocyanate compounds, hexaisocyanate compounds, and specifically, aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate. Polyisocyanate; alicyclic isocyanate compounds such as dicyclohexylmethane-4,4-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, hydrogenated xylylene diisocyanate; pentamethylene diisocyanate, hexa Methylene diisocyanate, heptamethylene diisocyanate Chromatography, tri-methyl-hexamethylene diisocyanate, and aliphatic isocyanate compounds such as lysine diisocyanate.

Also, modified products such as biurets and isocyanurates of these compounds, and adducts that are the reaction products of these compounds with non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, and castor oil. Can also be used.

Of these isocyanate compounds, aliphatic isocyanate compounds are preferred, aliphatic diisocyanate compounds are more preferred, and pentamethylene diisocyanate, hexamethylene diisocyanate, and heptamethylene diisocyanate are particularly preferred.
An isocyanate type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

Coated printing material of the present invention, together with isocyanate compounds as the crosslinking agent, containing a specific metal-based cross-linking accelerator.
As the metal-based crosslinking accelerator, bismuth crosslinking accelerator, a titanium-based crosslinking accelerator, vanadium-based crosslinking accelerator, zirconium crosslinking accelerator, aluminum-based crosslinking accelerator, and nickel-based cross-linking accelerator. In this , a bismuth type crosslinking accelerator is preferably used .

Bismuth-based crosslinking accelerator, titanium-based crosslinking accelerator, vanadium-based crosslinking accelerator, zirconium-based crosslinking accelerator, aluminum-based crosslinking accelerator, or nickel-based crosslinking accelerator are bismuth, titanium, vanadium, zirconium, aluminum, Or an organometallic compound of nickel, which is a compound having a structure such as an alkoxide, carboxylate, or chelate, and preferably includes an acetylacetone complex, acetylacetonate, octylic acid compound, or naphthenic acid compound of these metals. .

Specific examples of the acetylacetone complex metals, acetylacetone titanium, acetylacetone vanadium, acetylacetone zirconium, aluminum acetylacetonate, acetylacetone nickel and the like.
Specific examples of the acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate, vanadium acetylacetonate, zirconium acetylacetonate, aluminum acetylacetonate, and nickel acetylacetonate.

Specific examples of octyl acid compounds, 2-ethylhexyl bismuth, 2-ethylhexyl, nickel, etc. zirconium 2-ethylhexyl acid.
Specific examples of the naphthenic acid compounds, naphthenic bismuth, nickel naphthenate, and etc. naphthenate zirconium.
The said metal type crosslinking accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

In the coating agent for printing of the present invention, the content ratio of the polyester resin and the isocyanate compound as the crosslinking agent is 1 to 30 parts by mass of the isocyanate compound as the crosslinking agent with respect to 100 parts by mass of the polyester resin in solid ratio. Is preferable, 2-20 mass parts is more preferable, and 3-15 mass parts is especially preferable.

Moreover, in the coating agent for printing of this invention, the content rate of the isocyanate type compound as a crosslinking agent and the said metal type crosslinking accelerator is 100 mass parts of polyester resins, and the said metal type crosslinking accelerator is metal amount conversion. 0.001-5 mass parts is preferable, 0.005-2 mass parts is more preferable, and 0.01-1 mass part is especially preferable.

Coated printing material of the present invention, the polyester-based resin, isocyanate-based compounds as crosslinking agents, and the particular metal-based crosslinking accelerator other than may contain a diluent medium. Examples of the dilution medium include an organic dilution medium and an aqueous dilution medium, and an organic dilution medium is preferable.
Examples of the organic dilution medium include aromatic hydrocarbons such as toluene and xylene, aliphatic ketones such as methyl ethyl ketone and diethyl ketone, and organic solvents such as alicyclic ketones such as cyclohexanone. Can be used in combination. When combining 2 or more types, it is preferable to combine organic solvents having different boiling points of 10 to 60 ° C. in terms of improving the drying efficiency.

In the printing coating agent of the present invention, the content of resin solids such as an isocyanate compound as a polyester resin and a crosslinking agent is preferably 0.5 to 10% by mass, and preferably 1 to 7% by mass. More preferred.

In addition, various fillers such as organic fillers and inorganic fillers can be blended in the coating agent for printing of the present invention in order to improve slipperiness and obtain a matte feeling.
Examples of the organic filler include resin powder such as polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, acrylic resin such as methyl methacrylate, or a mixture thereof.

Examples of the inorganic filler include inorganic oxides such as silica and alumina, and metal powders such as gold powder and silver powder.
The blending amount of the filler is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin component of the printing coating agent and the crosslinking agent.

The coating agent for printing of the present invention preferably has a gel fraction of 50% or more, particularly preferably 60% or more after 14 days of coating. Below this range, the cohesive force of the coating agent for printing becomes insufficient, which may cause cohesive failure of the coating agent layer. Further, the ratio of the gel fraction after 14 days of coating to the gel fraction after 3 days of coating (gel fraction after 14 days of coating / gel fraction after 3 days of coating) is preferably within 4.5. Is more preferably within 2.5, and particularly preferably within 1.5. Below this range, the blocking resistance at the time of production may be insufficient.

Method for producing a coated printing film of the present invention, Ru is provided a coated printing material layer by applying the coated printing agent to the surface of the film substrate.
The coating amount of the coating agent for printing on the film substrate is usually such that the thickness of the coating layer for printing after drying is in the range of 10 to 600 nm, preferably in the range of 20 to 400 nm, particularly preferably in the range of 30 to 200 nm. Such an amount is preferred.

  Various plastic films can be used as the film substrate. Specific examples of the film substrate include, for example, polyolefin resins such as polyethylene resin and polypropylene resin, polyester resins such as polyethylene terephthalate resin, polyethylene naphthalate resin and polybutylene terephthalate resin, polyvinyl chloride resin, polystyrene resin, acrylonitrile-butadiene- Styrene copolymer resin (ABS resin), polyurethane resin, polycarbonate resin, polyamide resin, polyimide resin, poly (meth) acrylate, polybutene resin, polybutadiene resin, polymethylpentene resin, acrylic urethane resin, ethylene-vinyl acetate resin , Ethylene- (meth) acrylic ester resin, ionomer resin, thermoplastic elastomer resin, fluororesin, and mixtures of two or more of these Film or synthetic resin, two or more layers of laminated film of these same or different, and synthetic paper.

As a film base material, the film which consists of a polyester resin or polyolefin resin is preferable, and the film base material which consists of a polyethylene terephthalate resin, a polypropylene resin, or a polyethylene resin is mentioned more preferably.
Although there is no restriction | limiting in particular in the thickness of a film base material, 5-350 micrometers is preferable normally, 10-300 micrometers is more preferable, 15-250 micrometers is especially preferable.

Examples of the method for applying the printing coating agent to the film substrate include conventionally known methods such as bar coating, knife coating, roll coating, blade coating, and die coating.
In order to improve the adhesion of the printing coating agent to the film substrate, an anchor coat layer is provided on the surface of the film substrate as necessary, and the printing coat layer is provided on the surface of the anchor coating layer. Can do.

Examples of the anchor coat agent used for providing the anchor coat layer include a polyurethane anchor coat agent and a polyester anchor coat agent.
It is preferable to perform drying normally at 60-130 degreeC, and 80-120 degreeC is more preferable. The drying time is not particularly limited, but usually 10 seconds to 5 minutes is sufficient.

The coated film for printing obtained by the method for producing a coated film for printing according to the present invention can be used as an adhesive label by providing an adhesive layer on the back surface of the film substrate.
The back surface of the film substrate may be subjected to an easy adhesion treatment in order to further increase the adhesion with the pressure-sensitive adhesive layer. Although there is no restriction | limiting in particular as an easily bonding process, For example, a corona discharge process etc. are mentioned.

Various pressure-sensitive adhesives can be used as the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer. Specific examples of the adhesive include, for example, natural rubber-based adhesives, synthetic rubber-based adhesives, acrylic resin-based adhesives, polyvinyl ether resin-based adhesives, urethane resin-based adhesives, silicone resin-based adhesives, and the like. Preferably, an acrylic resin-based adhesive, a rubber-based adhesive, a silicone resin-based adhesive, etc. are used. Further, the pressure-sensitive adhesive may be a solvent-type pressure-sensitive adhesive, a water-type pressure-sensitive adhesive, or a strong pressure-sensitive adhesive or a re-peelable pressure-sensitive adhesive.

Moreover, you may provide a peeling sheet in the surface on the opposite side to the base film side of an adhesive layer.
The release sheet is not particularly limited. Examples of the base material of the release sheet include paper, synthetic paper, and synthetic resin film. As the paper, for example, a paper base such as fine paper, glassine paper, coated paper, a paper base such as a laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene to these paper bases, and high-quality paper, Examples thereof include a paper base or the like that is subjected to a sealing treatment with glassine paper, coated paper, etc. with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin, or the like. Examples of plastic synthetic resin films include films made of polyolefin resins such as polyethylene resins and polypropylene resins, films made of polyester resins such as polybutylene terephthalate resins and polyethylene terephthalate resins, and films obtained by subjecting these synthetic resin films to easy adhesion treatment. It is desirable that these are coated with a release agent.

Examples of the release agent include fluorine resins, silicone resins, olefin resins, and long-chain alkyl group-containing carbamates.
As the printing ink used for printing on the coating agent layer of the printing coat film obtained by the method for producing a printing coat film of the present invention, various inks such as an ultraviolet curable ink are used. As the ultraviolet curable ink, various ultraviolet curable inks are used, and polyacrylate ultraviolet curable inks are preferable.

  Next, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by these examples.

(Example 1)
(1) Preparation of coating agent for printing Urethane modified polyester resin having a basic structure of an aromatic polyester (manufactured by Toyobo Co., Ltd., trade name “Byron UR1700”, number average molecular weight 16000, hydroxyl value 19 mgKOH / g, acid value 26 mgKOH / G, glass transition temperature 92 ° C. 70 parts by mass, urethane-modified polyester resin having a basic structure of an aromatic polyester (manufactured by Toyobo Co., Ltd., trade name “Byron UR8700”, number average molecular weight 32000, hydroxyl value 2-4 mg KOH / G, acid value of less than 1 mg KOH / g, glass transition temperature -22 ° C. 30 parts by mass, hexamethylene diisocyanate (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, bismuth-based crosslinking accelerator ( Product name “Pucat 25”, manufactured by Nippon Chemical Industry Co., Ltd. And 25 parts by mass) 0.05 part by mass, and 900 parts by mass of toluene, 900 parts by mass of methyl ethyl ketone, and 90 parts by mass of cyclohexanenone as a solvent were mixed to obtain a coating agent for printing.

(2) Preparation of coating film for printing The coating agent for printing obtained in (1) above is dried on the surface of a polyester resin film (trade name “Lumirror PET50 T-60”, manufactured by Toray Industries, Inc., thickness 50 μm). The film was applied by bar coating in such an amount that the subsequent thickness was 100 nm, and dried for 1 minute with a hot air dryer at 90 ° C. to prepare a coated film for printing.

(3) Creation of printing film with pressure-sensitive adhesive layer Glassine paper, product with strong adhesive acrylic pressure-sensitive adhesive (product of Lintec, trade name “PA-T1”) peel-treated with a silicone resin (product of Lintec) Using a roll knife coater on the release surface of the name “SP-8K Ao”), the coating thickness after each drying was applied to 20 μm, and dried at 90 ° C. for 2 minutes. Formed. After drying, the pressure-sensitive adhesive layer on the release sheet was bonded to the back surface of the polyester resin film of the printing film prepared in the above (2) to prepare a printing pressure-sensitive adhesive sheet.

(Example 2)
In Example 1 (1), the compounding amount of the bismuth-based crosslinking accelerator (trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.) was changed to 0.30 parts by mass instead of 0.05 parts by mass. Produced a coated film for printing and a pressure-sensitive adhesive sheet for printing in the same manner as in Example 1.

(Example 3)
In Example 1 (1), the blending amount of the bismuth-based cross-linking accelerator (manufactured by Nippon Chemical Industry Co., Ltd., trade name “Pucat 25”) was changed to 1.00 mass parts instead of 0.05 mass parts. Produced a coated film for printing and a pressure-sensitive adhesive sheet for printing in the same manner as in Example 1.

Example 4
In Example 2 (1), Example 2 was used except that the amount of hexamethylene diisocyanate (trade name “Coronate HL” manufactured by Nippon Polyurethane Co., Ltd.) was changed to 5 parts by mass instead of 3 parts by mass. A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner.

(Example 5)
In Example 1 (1), printing was carried out in the same manner as in Example 1 except that 1.5 parts by mass of silica filler (trade name “Aerosil 200”, average particle diameter of 12 nm, manufactured by Nippon Aerosil Co., Ltd.) was blended. Coating film and printing pressure-sensitive adhesive sheet were prepared.

(Example 6)
In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (trade name “Pucat 25”, manufactured by Nippon Chemical Industry Co., Ltd.), a vanadium-based crosslinking accelerator (acetylacetone vanadium, Nippon Chemical Industry Co., Ltd.) Coated film for printing in the same manner as in Example 1 except that the product name is “Narsemvanadil”, 19% by mass in terms of metal), 0.40 part by mass, and 3 parts by mass of silica filler is blended. A pressure-sensitive adhesive sheet for printing was prepared.

(Example 7 )
In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.), an aluminum-based crosslinking accelerator (acetylacetone aluminum, Nippon Chemical Industry Co., Ltd.) A coated film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 1 except that the product name was “Nursem Aluminum” (8% by mass in terms of metal amount) and 1.00 parts by mass. Created.

(Example 8 )
A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 6 except that the silica filler was not blended in (1) of Example 6.

(Example 9 )
In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.), a nickel-based crosslinking accelerator (nickel octylate metal soap) Manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name “Nikka Octix Nickel, 11% by mass in terms of metal amount) 0.80 parts by mass, in the same manner as in Example 1, except that the coating film for printing, printing An adhesive sheet was prepared.

(Example 10 )
In Example 2 (2), an oriented polypropylene resin film (OPP, manufactured by Toray Industries, Inc., trade name “Toray Co., Ltd., trade name“ Lumirror PET50 T-60 ”, thickness 50 μm)” was used instead of the polyester resin film (trade name “Lumirror PET50 T-60”, thickness 50 μm). DOO Refan BO # 50 ", except for using the thickness 50 [mu] m) in a similar manner as in example 2, was prepared coated printing film, the printing pressure-sensitive adhesive sheet.

(Example 11 )
In Example 3 (2), an oriented polypropylene resin film (OPP, manufactured by Toray Industries, Inc., trade name “Toray, Inc., trade name“ Lumirror PET50 T-60 ”, thickness 50 μm)” was used instead of the polyester resin film (trade name “Lumirror PET50 T-60”, thickness 50 μm). DOO Refan BO # 50 ", except for using the thickness 50 [mu] m) in a similar manner as in example 3, was prepared for printing coated film, printing adhesive sheet.

(Comparative Example 1)
In Example 1 (1), a printing film was prepared in the same manner as in Example 1 except that no crosslinking accelerator was added.

(Comparative Example 2)
In Example 1 (1), a printing film was produced in the same manner as in Example 1 except that the crosslinking agent and the crosslinking accelerator were not blended.
The gel fraction of the coating agent layer, the adhesion between the film substrate and the coating agent layer, the printing adhesion, the blocking resistance and the thermal transfer printing property were evaluated and evaluated by the methods shown below. The results are shown in Tables 1-3.

(1) Measurement of gel fraction of coating agent layer The coating agent for printing obtained in Examples and Comparative Examples was applied to the surface of the release sheet so that the film thickness after drying was 2 μm, and 23 ° C., 50 The coating agent layer after 3 days and 14 days was peeled off from the release sheet for 3 days and 14 days at% RH, and a coating agent layer for gel fraction measurement was prepared. The obtained coating agent layer was immersed in toluene at 23 ° C. for 72 hours, undissolved components were dried at 120 ° C. for 3 hours, and left to stand at 23 ° C. and 50% relative humidity for 3 hours to adjust the humidity. Then, the mass was measured, and the gel fraction was calculated by the following formula.
Gel fraction (% by mass) = (mass of undissolved component after immersion / drying / mass of coating agent layer before immersion) × 100
Further, based on the obtained gel fraction, the ratio of the gel fraction after 14 days of coating to the gel fraction after 3 days of coating (gel fraction after 14 days of coating / gel fraction after 3 days of coating). ) Was calculated.

(2) Evaluation of adhesion between film base material and coating agent layer The surface of the coating agent layer obtained in Examples and Comparative Examples was subjected to a cross cut having a 1 mm width in a grid pattern, and the cross cut was performed in the grid pattern. Adhesive tape (made by Nichiban Co., Ltd., trade name “Cellotape”) is pasted on the surface of the coating agent layer, and a cellotape peel test is performed in accordance with the cross-cut tape method of JIS K5600-5-6 (cross-cut method). The adhesion between the film substrate and the coating agent layer was evaluated based on the above criteria.
A: The number of cells in which the coating agent layer remains after the cellophane peeling test is 95 or more per 100 cells.
(Circle): The number of squares in which a coating agent layer remains after a cellophane peeling test is 90 or more and 94 or less per 100 squares.
X: The number of squares in which the coating agent layer remains after the cellophane peeling test is less than 90 per 100 squares.

(3) Evaluation of printing adhesiveness of coating agent layer On the surface of the coating agent layer obtained in Examples and Comparative Examples, ultraviolet curable ink for printing (manufactured by T & K TOKA Corporation, trade name “BEST CURE UV161 ink S” )) Using a printing machine (trade name “RI Tester”, manufactured by Akira Seisakusho Co., Ltd.), and ultraviolet rays are irradiated with a high-pressure mercury lamp to cure the ink. Formed. The surface of the printed layer is cross-cut with a 1 mm width in a grid pattern, and an adhesive tape (trade name “Cello Tape”, manufactured by Nichiban Co., Ltd.) is pasted on the surface of the cross-cut print layer. JIS K5600- A cello tape peeling test was conducted in accordance with the grid tape method of 5-6 (cross cut method), and the printing adhesion of the coating agent layer was evaluated according to the following criteria.

(Double-circle): The number of the squares in which a printing layer remains after a cellophane peeling test is 95 or more per 100 squares.
(Circle): The number of the grids where a printing layer remains after a cellophane peeling test is 90 or more and 94 or less per 100 grids.
X: The number of squares in which the printed layer remains after the cellophane peeling test is less than 90 per 100 squares.

(4) Evaluation of blocking resistance The film base of the coating film for printing was applied to the surface of the coating agent layer of the coating film for printing 3 hours after coating the coating film for printing obtained in Examples and Comparative Examples. Five printed coat films were stacked so that the surfaces of the materials overlapped, and then sandwiched between glass plates. A load of 80 g / cm ² was applied from above the five coated film for printing, and the film was left in an environment of 60 ° C. and 95% RH or 70 ° C. and 30% RH for 3 days. Then, after standing for 24 hours in an environment of 23 ° C. and 50% RH, the overlapped printing coat film is peeled off, and the surface of the coating agent layer of the printing coat film and the film base of the adjacent printing coat film are removed. The adhesiveness with the back surface of the material was evaluated according to the following criteria.

A: There is no adhesion between the surface of the coating agent layer and the surface of the film substrate.
○: The surface of the coating agent layer and the surface of the film base material are adhered to each other at a point, but both can be easily removed by hand, and the surface of the coating agent layer after peeling is not visually changed at all. .
X: The surface of the coating agent layer and the surface of the film base material are adhered, and both cannot be peeled by hand, or both can be peeled by hand, but the surface of the coating agent layer after peeling Is not smooth and changes visually.

(5) Evaluation of thermal transferability A resin-based ink ribbon (product name “TR4070”, manufactured by Sony Chemical Co., Ltd.) is applied to the surface of the coating agent layer of the coating film for printing obtained in Examples and Comparative Examples. Manufactured, model name “Zebra140XIIII”) at a speed of 3 inches / sec (7.6 cm / sec). The thermal transferability of the ink ribbon was evaluated according to the following criteria.
○: Ink ribbon can be transferred without problems.
Δ: Transfer of the ink ribbon is possible, but voids and rubbing occur on the printed matter.
X: Ink ribbon cannot be transferred.

In addition, in the said Tables 1-3, the compounding quantity of a compounding component is shown by the mass part.

Claims (7)

  A polyester resin having a glass transition temperature of 40 to 105 ° C., a polyester resin having a glass transition temperature lower by 20 ° C. or more than the glass transition temperature of the polyester resin, an isocyanate compound as a crosslinking agent, and a bismuth crosslinking Containing at least one metal-based crosslinking accelerator selected from an accelerator, a titanium-based crosslinking accelerator, a vanadium-based crosslinking accelerator, a zirconium-based crosslinking accelerator, an aluminum-based crosslinking accelerator, and a nickel-based crosslinking accelerator. Characteristic coating agent for printing.   The printing coating agent according to claim 1, wherein the mixing ratio of the polyester resin having a glass transition temperature lower by 20 ° C or more is 1 to 50% by mass with respect to the total mass of all the polyester resins.   The coating agent for printing according to claim 1 or 2, wherein the isocyanate compound is hexamethylene diisocyanate.   The coating agent for printing according to any one of claims 1 to 3, wherein the polyester resin is a urethane-modified polyester resin. The printing coating agent according to claim 1, a method of manufacturing a printed coat film characterized in that applied to the surface of the film substrate Ru provided for printing coating agent layer. The method for producing a coated film for printing according to claim 5, wherein the film base material is a film base material made of polyethylene terephthalate resin, polypropylene resin or polyethylene resin. The manufacturing method of the coating film for printing of Claim 5 or Claim 6 with which the adhesive layer is provided in the back surface of the said film base material.