JP2009084420A - Method for producing adhesive tape or adhesive sheet - Google Patents

Abstract

A method for manufacturing a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive tape having characters and images, and a method for manufacturing a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive tape capable of handling a small lot and having a high-quality image.
A colored ink composition comprising: a step of ejecting a radiation curable colored ink composition onto a support to form a colored image; and a step of irradiating the ejected ink composition with radiation. A pressure-sensitive adhesive tape comprising a colorant, a polymerizable compound and a photopolymerization initiator, wherein the glass transition temperature of the cured film of the polymerizable compound alone contained in the colored ink composition is 25 ° C. or lower Or the manufacturing method of an adhesive sheet.
[Selection figure] None

Description

  The present invention relates to a method for producing an adhesive tape or an adhesive sheet.

Conventionally, (meth) acrylic polymers are known as pressure-sensitive adhesives that are self-adhesive and have good heat resistance and weather resistance. In addition, it is known that a photopolymerizable composition is applied to the entire surface using a bar coater, roll coater, etc. as a method for producing an adhesive sheet, and cured by irradiation with ultraviolet rays to obtain an acrylic pressure-sensitive adhesive layer. Yes.

Various reports have been made on pressure sensitive adhesives, such as acrylic esters of monohydric alcohols (where the homopolymer has a Tg lower than 0 ° C.) and nonpolar ethylenically unsaturated monomers (provided that The homopolymer has a solubility parameter not greater than 10.50 and a Tg greater than 15 ° C.) and a polar ethylenically unsaturated monomer (provided that the homopolymer has a solubility parameter greater than 10.50 and 15 ° C. A pressure sensitive adhesive which is a polymerization product with a higher Tg is disclosed (see Patent Document 1).
In addition, an adhesive polymer having a (meth) acrylic acid ester component unit as a main structural unit and a weight average molecular weight of 50,000 or more and a (meth) acrylic acid ester component unit as a main structural unit and a weight average molecular weight of 20 A pressure-sensitive adhesive composition containing a tackifying resin having a molecular weight of 1,000 or less and a monomer mainly composed of (meth) acrylic acid ester and containing substantially no solvent is disclosed (see Patent Document 2). .
There is also known a method of forming a pressure sensitive adhesive in a pattern using flexographic printing or screen printing.

  On the other hand, the inkjet method has attracted attention in recent years as an inexpensive device and does not require a plate at the time of printing, and can be patterned only in the required portion, and pressure sensitive adhesive is patterned by the inkjet method. Techniques include: (a) providing a curable fluid composition that forms a pressure sensitive adhesive upon curing, (b) inkjet printing the composition onto at least a portion of the substrate, and (c) A method of forming a pressure-sensitive adhesive composition on a substrate is disclosed, which includes a step of curing the composition under conditions effective to form a pressure-sensitive adhesive (see Patent Document 3). .

  On the other hand, when printing a character and an image on an adhesive sheet and an adhesive tape, after producing an adhesive sheet, it prints on the surface opposite to an adhesive layer by a separate process using a conventionally known printing method.

Japanese National Patent Publication No. 10-509198 JP 2001-49200 A JP-T-2004-519536

  An object of the present invention is to provide a pressure-sensitive adhesive tape having a high-quality image and a method for manufacturing a pressure-sensitive adhesive sheet that can be applied to a small lot in a method for manufacturing a pressure-sensitive adhesive tape and a pressure-sensitive adhesive sheet having characters and images.

The above-described problems of the present invention have been solved by the means described in <1> below. It is described below together with <2> to <5> which are preferred embodiments.
<1> A step of forming a colored image by discharging a radiation-curable colored ink composition on a support, and a step of irradiating the discharged ink composition with radiation, wherein the colored ink composition is A pressure-sensitive adhesive tape containing a colorant, a polymerizable compound, and a photopolymerization initiator, and having a glass transition temperature of a cured film of a polymerizable compound alone contained in the colored ink composition of 25 ° C. or lower Production method of adhesive sheet,
<2> The method further includes a step of discharging a radiation-curable colorless ink composition onto a region of the support on which a colored image is not formed, and a step of irradiating the discharged colorless ink composition with radiation. The method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet according to the above <1>, wherein the colorless ink composition contains a polymerizable compound and a photopolymerization initiator and does not contain a colorant,
<3> The method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet according to the above <2>, wherein the glass transition temperature of the cured film containing the polymerizable compound alone contained in the colorless ink composition is 25 ° C. or lower.
<4> The method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet according to any one of <1> to <3> above, wherein the support is a transparent support.
<5> The above <1>, further comprising a step of overlaying a second support having a peelable layer after the step of discharging the colored ink composition to form an image and before the step of irradiating radiation. -The manufacturing method of the adhesive tape or adhesive sheet as described in any one of said <4>.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the adhesive tape which has a character and an image, and the manufacturing method of an adhesive sheet which can respond to a small lot and has a high quality image could be provided.

The method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention comprises a step of discharging a radiation-curable colored ink composition onto a support to form a colored image, and irradiating the discharged ink composition with radiation. The colored ink composition contains a colorant, a polymerizable compound, and a photopolymerization initiator, and the glass transition temperature of the cured film of the polymerizable compound alone contained in the colored ink composition is 25 ° C. or lower. It is characterized by being.
Further, the method further includes a step of discharging a radiation-curable colorless ink composition onto a region of the support on which a colored image is not formed, and a step of irradiating the discharged colorless ink composition with radiation. The ink composition preferably contains a polymerizable compound and a photopolymerization initiator and does not contain a colorant. Moreover, it is preferable that the glass transition temperature of the cured film only by the polymeric compound contained in a colorless ink composition is 25 degrees C or less.
Hereinafter, the present invention will be described in detail.

(Colored ink composition and colorless ink composition)
Colored ink composition and colorless ink composition used in the present invention (hereinafter collectively referred to as “ink composition”. In the present invention, “ink composition” is also simply referred to as “ink”). ).
In the present invention, the colored ink composition contains a colorant, a polymerizable compound, and a photopolymerization initiator. The colorless ink composition contains a polymerizable compound and a photopolymerization initiator and does not contain a colorant.
In the present invention, the ink composition is an ink composition that can be cured by radiation, and is an oil-based ink composition.
The term “radiation” as used in the present invention is not particularly limited as long as it is an actinic radiation that can impart energy capable of generating a starting species in the ink composition by the irradiation, and widely includes α rays, γ rays, X Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays and electron beams are particularly preferable from the viewpoints of curing sensitivity and device availability. Therefore, in the present invention, the ink composition is preferably an ink composition that can be cured by irradiating ultraviolet rays as radiation.

<Polymerizable compound>
In the present invention, the ink composition (colored ink composition and colorless ink composition) contains a polymerizable compound. The polymerizable compound that can be used is preferably an addition polymerizable compound, and more preferably a radical polymerizable compound or a cationic polymerizable compound.
Moreover, the polymeric compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types, for example, may use together a radically polymerizable compound and a cationically polymerizable compound. Good.

  This polymerizable compound is polymerized by this polymerization rather than a system containing the polymer itself, because it undergoes a polymerization reaction upon irradiation with radiation (active energy rays) by the action of a polymerization initiator described later and cures itself. At the same time as the adhesive force with the support that comes into direct contact is increased, the colored ink composition has a Tg of 25 ° C. or lower when it becomes a polymer so as to be highly adhered to the support. The adhesion between the substrate and the support can be effectively increased. Therefore, the image recorded on the support can be prevented from being peeled off due to external force, and a robust image can be formed.

  In addition, it can improve the resistance (light resistance, ozone resistance) against light and oxidizing gas (especially ozone) of images recorded on an arbitrarily selected support, which is also effective in improving scratch resistance. is there.

In the colored ink composition, the polymerizable compound has a glass transition temperature of 25 ° C. or lower, preferably 0 ° C. or lower, and a glass transition temperature lower than that of a cured film obtained by curing the polymerizable compound. It is preferable. It is more preferably −20 ° C. or less, further preferably −30 ° C. or less, particularly preferably −50 ° C. or less, and in consideration of use in a freezer, it is −100 ° C. or less. Preferably there is.
When the glass transition temperature of the cured film exceeds 25 ° C., sufficient adhesion between the support and the ink composition cannot be obtained. Moreover, sufficient adhesiveness cannot be obtained.
Further, the glass transition temperature of the colorless ink composition is preferably 25 ° C. or lower as in the case of the colored ink composition, and the more preferable range is also the same.

In the present invention, the glass transition point may be 25 ° C. or less in a state where several kinds of polymerizable compounds are combined.
In addition, "the glass transition temperature of the cured film only by a polymeric compound" means the glass temperature of the cured film obtained by making it harden | cure by radiation irradiation using only a polymeric compound and a polymerization initiator.
The glass transition temperature (Tg) when the cured film (polymer) is formed is the value when it is described in the manufacturer's measurement value or literature (for example, “Photo-curing technology data book” by Kunihiro Ichimura).
If the glass transition temperature (Tg) is unknown, a polymerizable compound and a polymerization initiator are mixed, applied with a bar coater to a thickness of 100 μm, and cured with a metal halide lamp to produce a polymer. To do.
5 mg of the obtained polymer is sampled, and the sampled polymer sample (sample) is measured at a measurement temperature range of −100 ° C. to 150 ° C. using a differential scanning calorimetry apparatus (Differential Scanning Calorimetry, DSC). be able to. The glass transition temperature of the cured film is measured by, for example, a method (DSC method) defined in ASTM D3418-82.

When a plurality of polymerizable compounds are used in combination, the glass transition temperature of each polymerizable compound alone is determined by the above method, and a value calculated based on the following formula is used.
1 / Tg = W1 / T1 + W2 / T2 + W3 / T3 +
here,
Tg: Glass transition temperature (absolute temperature) of a plurality of polymerizable compounds
W1, W2, W3 ..:% by weight of a specific monomer in the polymerizable composition
T1, T2, T3 ..: Glass transition temperature (absolute temperature) of a single polymer composed of the monomer
It is.

[Radically polymerizable compound]
The radically polymerizable compound that can be suitably used in the present invention will be described in detail.
In the present invention, the ink composition can use a radical polymerizable compound as one of the polymerizable compounds, and the radical polymerizable compound is more preferably an ethylenically unsaturated compound. Further, it preferably contains at least one polymerizable compound monomer that forms a cured film (polymer) having a glass transition temperature (Tg; hereinafter sometimes abbreviated as “Tg”) of 25 ° C. or less by polymerization, More preferred is (meth) acrylate ((meth) acrylic acid ester).
Here, “(meth) acrylate” refers to both and / or “acrylate” and “methacrylate”, and “(meth) acryl” refers to both and / or “acryl” and “methacryl”.

  Examples of preferable monofunctional (meth) acrylate monomers include methyl (meth) acrylate, isooctyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, isoamyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, benzyl (meth) acrylate, sec-butyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) Acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate And a mixture thereof, and the like, but not limited thereto. Particularly preferred monofunctional (meth) acrylate monomers include isooctyl (meth) acrylate, isononyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, Examples thereof include those selected from n-butyl (meth) acrylate, sec-butyl (meth) acrylate, mixtures thereof and the like.

  Further, it is preferable to include a bifunctional and polyfunctional (meth) acrylate radical polymerizable monomer, such as alkanediol, alkanetriol, alkanetetraol, etc. (for example, 1,4-butanediol di (meth)). And ester derivatives of acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate). US Patent No. Bifunctionals such as 1,2-ethanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, and pentaerythritol tetra (meth) acrylate described in US Pat. No. 4,379,201 (Heilmann et al.) Polyfunctional (meth) acrylate monomers can also be used in the present invention.

  In the present invention, a polymerizable compound monomer that forms a cured film (polymer) having a glass transition temperature of 25 ° C. or higher by polymerization is also preferably used in a range where the glass transition temperature of the mixed composition is 25 ° C. or lower. Specifically, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentaenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-acryloyl Roxyethyl (meth) acrylate, bisphenol A di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol didi (meth) acrylate, tripropylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dimethylolpropane tetrameth) acrylate, dipentaerythritol Hexa (meth) known radical polymerizable or crosslinkable monomers in the industry, such as acrylate, and oligomers.

  In the present invention, vinyl ester monomers are also preferably used. Particular preference is given to monofunctional unsaturated vinyl esters of straight-chain or branched carboxylic acids containing 1 to 16 carbon atoms, such vinyl ester monomers being vinyl acetate, vinyl 2-ethylhexanoic acid , Vinyl caproate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, and vinyl octoate. Particularly preferred vinyl ester monomers include vinyl laurate, vinyl caproate, 2- And vinyl ethylhexanoate, and mixtures thereof.

  In the present invention, a vinyl ether compound can also be used as the radical polymerizable compound. Examples of suitable vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, hexanediol divinyl ether, combinations thereof, and the like.

  Other radical polymerizable compounds that can be suitably used in the present invention include moieties or substituents that can be readily copolymerized with (meth) acrylate and vinyl ester monomers and that significantly absorb radiation at the wavelength of the selected actinic radiation source. A monofunctional monomer containing almost no groups can be mentioned. Examples of such monomers include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, sulfoethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylamide, N- (t -Butyl) (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include, but are not limited to, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and mixtures thereof. Of these, (meth) acrylic acid, N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof are particularly preferred.

  In the present invention, the molecular weight of the radical polymerizable compound (monomer) is 200 or more and 2,000 or less (in the present invention, “200 or more and 2,000 or less” is also referred to as “200 to 2,000”). The same applies hereinafter.), Preferably 300 to 1,200, more preferably 500 to 1,000. By making the molecular weight of a radically polymerizable compound into the said range, since adhesiveness with respect to a support body can be improved effectively and still more favorable adhesiveness can be obtained, it is preferable.

[Cationically polymerizable compound]
Although it does not specifically limit as said cation polymeric compound, The above-mentioned vinyl ether type compound, an epoxy resin, an oxetane type compound, an episulfide type compound, an ethyleneimine type compound, etc. are mentioned. Of these, epoxy resins and oxetane compounds are preferably used.

  Specific examples of the epoxy resin include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy Novolac epoxy resins such as resins; trisphenol methane triglycidyl ether and the like, and aromatic epoxy resins such as hydrogenated products and halides thereof; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3 , 4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, bis ( , 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta An alicyclic epoxy resin such as dioxane, bis (2,3-epoxycyclopentyl) ether, trade name “EHPE-3150” (softening temperature: 71 ° C.) manufactured by Daicel Chemical Industries; Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 2-9 carbon atoms, Like Is an aliphatic epoxy resin such as polyglycidyl ether of a long-chain polyol containing polyoxyalkylene glycol having 2 to 4 alkylene groups, polytetramethylene ether glycol, etc .; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Diglycidyl ester of hexahydrophthalic acid, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, glycidyl ester of dimer, glycidyl ester type epoxy resins such as hydrogenated products thereof; triglycidyl isocyanurate, cyclic N, N′-diglycidyl derivatives of alkylene urea, N, N, O-triglycidyl derivatives of p-aminophenol, N, N, O-triglycidyl derivatives of m-aminophenol, etc. Glycidylamine type epoxy resins such as these hydrogenated products; Copolymers of glycidyl (meth) acrylate and radical polymerizable monomers such as ethylene, vinyl acetate and (meth) acrylate; for example, epoxidized polybutadiene An epoxidized unsaturated carbon double bond of a polymer mainly composed of a conjugated diene compound or a polymer mainly composed of a partially hydrogenated conjugated diene compound; for example, epoxidized SBS Block copolymer having a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a polymer block mainly composed of a partial hydrogenated product of a conjugated diene compound in the same molecule Epoxidized unsaturated carbon double bond of one conjugated diene compound; 1 molecule A polyester resin having at least one epoxy group; a urethane-modified epoxy resin or a polycaprolactone-modified epoxy resin in which a urethane bond or a polycaprolactone bond is introduced into the structure of the above various epoxy resins; NBR, CTBN, Examples thereof include rubber-modified epoxy resins containing rubber components such as polybutadiene and acrylic rubber. These epoxy resins may be used alone as a polyfunctional epoxy resin or a monofunctional epoxy resin, or two or more types may be used in combination.

  Examples of particularly preferred epoxy resins include polyglycidyl ethers of long-chain polyols including polyoxyalkylene glycols having 2 to 9 carbon atoms, preferably 2 to 4 alkylene groups, and polytetramethylene ether glycol. An aliphatic epoxy resin can be illustrated.

  Oxetane compounds can also be used suitably. Specific examples of preferable single-tube oxetane include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4- Fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3- Oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ) Ether, 2-ethylhexyl (3-ethyl-3-oxeta) Methyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl ( 3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Examples of the polyfunctional oxetane include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis. -(3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1, 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, tri Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl) -3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3- Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3 -Oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl) 3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis ( 3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis ( 3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl) And polyfunctional oxetanes such as ru-3-oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

  In the present invention, when the ink composition contains a cationic polymerizable compound, the blending ratio of the polyfunctional cationic polymerizable compound and the monofunctional cationic polymerizable compound is monofunctional with respect to 100 parts by weight of the polyfunctional cationic polymerizable compound. It is preferable that it is 20-200 weight part of cationically polymerizable compounds.

<Photopolymerization initiator>
In the present invention, the ink composition contains a photopolymerization initiator. When a radical polymerizable compound is used as the polymerizable compound, it is preferable to use at least a radical polymerization initiator. When a cationic polymerizable compound is used as the polymerizable compound, at least a cationic polymerization initiator is used. It is preferable.
A radical polymerization initiator and a cationic polymerization initiator can also be used in combination.

  The radical polymerization initiator or cationic polymerization initiator in the present invention is a compound that generates a radical, acid, or base by causing a chemical change through the action of light or interaction with the electronically excited state of a sensitizing dye. Among them, a photo radical generator or a photo acid generator is preferable from the viewpoint that polymerization can be initiated by a simple means of exposure.

  In the present invention, a radical polymerization initiator or a cationic polymerization initiator can be appropriately selected and used from the photopolymerization initiators described in detail below. A photoinitiator can also be used individually by 1 type and may use 2 or more types together.

  As the photopolymerization initiator, actinic rays to be irradiated, for example, 400 to 200 nm ultraviolet rays, far ultraviolet rays, g rays, h rays, i rays, KrF excimer laser rays, ArF excimer laser rays, electron beams, X rays, molecules Those having sensitivity to a line or an ion beam can be appropriately selected and used.

  As the specific photopolymerization initiator, those known to those skilled in the art can be used without limitation, and specifically, for example, Bruce M. et al. Monroe et al., Chemical Review, 93, 435 (1993). R. S. By Davidson, Journal of Photochemistry and biologic A: Chemistry, 73.81 (1993). J. P. Faussier “Photoinitiated Polymerization—Theory and Applications”: Rapra Review vol. 9, Report, Rapra Technology (1998). M. Tsunooka et al. , Prog. Polym. Sci. , 21, 1 (1996). Many are described. There are many chemical amplification type photoresists and compounds used for photocationic polymerization described in (Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187-192). Has been. Further, F.I. D. Saeva, Topics in Current Chemistry, 156, 59 (1990). G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993). H., et al. B. Shuster et al, JACS, 112, 6329 (1990). I. D. F. Eaton et al, JACS, 102, 3298 (1980). A group of compounds that undergo oxidative or reductive bond cleavage through interaction with the electronically excited state of the sensitizer as described in the above.

[Radical polymerization initiator]
In the present invention, a known radical polymerization initiator can be used as the photopolymerization initiator. The radical polymerization initiator that can be used in the present invention may be used alone or in combination of two or more. Moreover, you may use together a radical polymerization initiator and the cationic polymerization initiator mentioned later.
In the present invention, the radical polymerization initiator that can be used in the ink composition is a compound that absorbs external energy to generate radical polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

  The radical polymerization initiator that can be used in the present invention includes (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, and (e) thio compounds. (F) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) carbon halogen bond And (m) an alkylamine compound. These radical polymerization initiators may use the above compounds (a) to (m) alone or in combination. The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

  Preferred examples of (a) aromatic ketones, (b) acylphosphine compounds, and (e) thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. FOUASSIER J.M. F. RABEK (1993), pp. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117. More preferable examples include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, α-substituted benzoin compounds described in JP-B-47-22326, Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, JP-A Benzoin ethers described in JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318,791, α-aminobenzophenones described in European Patent 0284561A1, JP-A-2-21152 P-Di (dimethylaminobenzoyl) benze Thio-substituted aromatic ketones described in JP-A-61-194062, acylphosphine sulfides described in JP-B-2-9597, acylphosphines described in JP-B-2-9596, and JP-B-63-61950 Thioxanthones, and coumarins described in JP-B-59-42864.

  (C) As aromatic onium salt compounds, elements of Groups 15, 16 and 17 of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se, Te, or I fragrances Group onium salts are included. For example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, and 297443 are disclosed. The diazonium salts described in the specifications of U.S. Pat. Nos. 2,974,279, 279210, and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,444, and 2,833,827. Benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, US Pat. No. 4,743,528, JP-A-63) -138345, JP-A-63 142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. The compounds described in Japanese Patent Publication Nos. 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  (D) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 3,3 ′, 4,4′-tetra- ( t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-hexylperoxycarbonyl) ) Benzophenone, 3,3 ′, 4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (cumylperoxycarbonyl) benzophenone, 3,3 ′, Perester ester compounds such as 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate Thing is preferable.

  (F) Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2 , 2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 ' Tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 Examples include ', 5,5'-tetraphenylbiimidazole.

  (G) Examples of the ketoxime ester compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane-3. -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  (H) Examples of the borate compound include compounds described in US Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, and 109,773. Can be mentioned.

  (I) Examples of azinium compounds include those disclosed in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, and JP-B-46-42363. The compound group which has NO bond of each gazette description can be mentioned.

  (J) Examples of metallocene compounds include titanocenes described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. Examples thereof include iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  (K) Examples of the active ester compound include the specifications of European Patent Nos. 0290750, 046083, 156153, 271851, and 0388343, U.S. Pat. Nos. 3,901,710, and 4,181,531. Nitrobenzol ester compounds described in JP-A-60-198538 and JP-A-53-133022, European Patents 0199672, 84515, 199672, 0441115, and 0101122. No. 4,618,564, U.S. Pat. No. 4,371,605, and U.S. Pat. No. 4,431,774, JP-A 64-18143, JP-A 2-245756, and JP-A-4-365048. Iminosulfonate compound, Japanese Examined Patent Publication No. 62-6223, Japanese Examined Publication No. 63 No. 14340, and compounds, and the like described in the JP-A No. 59-174831.

  (L) Preferable examples of the compound having a carbon halogen bond include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, Examples thereof include compounds described in Japanese Utility Model Publication No. 53-133428, compounds described in German Patent No. 3337024, and the like.

  Further, compounds described in J. Org. Chem., 29, 1527 (1964) by FC Schaefer et al., Compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and the like can be mentioned. it can. A compound as described in German Patent No. 2641100, a compound described in German Patent No. 3333450, a compound group described in German Patent No. 3021590, or a compound group described in German Patent No. 3021599, etc. Can be mentioned.

In the ink composition used in the present invention, the total use amount of the radical polymerization initiator is preferably 0.01 to 35% by weight, more preferably 0.5 to 20%, based on the total use amount of the polymerizable compound. % By weight, more preferably in the range of 1.0 to 15% by weight. The ink composition can be cured at 0.01% by weight or more, and a cured film having a uniform degree of curing can be obtained at 35% by weight or less, which is preferable.
Moreover, when using the sensitizing dye mentioned later for the ink composition used for this invention, the total usage-amount of a radical polymerization initiator is the weight ratio of radical polymerization initiator: sensitizing dye with respect to a sensitizing dye. The range is preferably 200: 1 to 1: 200, more preferably 50: 1 to 1:50, and still more preferably 20: 1 to 1: 5.

(Cationic polymerization initiator)
As the cationic polymerization initiator (photoacid generator) that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization is used (Organic Electronics Materials Research Group, “For Imaging”). “Organic materials”, Bunshin Publishing (1993), pages 187-192). Examples of the cationic polymerization initiator suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ and CF ₃ SO ₃ ⁻ salts of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium are listed. be able to. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, an iron allene complex can be mentioned.

  The cationic polymerization initiator that can be used in the present invention may be used alone or in combination of two or more. In the present invention, the cationic polymerization initiator is preferably contained in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. is there.

  Examples of cationic polymerization initiators [(b-1) to (b-96)] suitably used in the present invention are listed below, but the present invention is not limited thereto. In some of the chemical structural formulas in the present invention, the hydrocarbon chain is described by a simplified structural formula in which symbols of carbon (C) and hydrogen (H) are omitted.

<Colorant>
In the present invention, the colored ink composition contains a colorant.
The colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used. In the present invention, a colorant that can be suitably used in the colored ink composition is selected from compounds that do not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction, from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. It is preferable.

[Pigment]
Although it does not necessarily limit as a pigment which can be used for this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used.
Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36,
Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22,27,28,29,36,60 as a blue or cyan pigment ,
As a green pigment, Pigment Green 7, 26, 36, 50,
As yellow pigments, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137 , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193,
As the black pigment, Pigment Black 7, 28, 26,
As a white pigment, Pigment White 6, 18, 21
Can be used according to the purpose.

[Oil-soluble dye]
Below, the oil-soluble dye which can be used by this invention is demonstrated.
The oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the weight of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.

  Among the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Examples include methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye species such as quinophthalone dyes, nitro / nitroso dyes, acridines And dyes and acridinone dyes.

  Of the oil-soluble dyes usable in the present invention, any magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Among the oil-soluble dyes applicable to the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes;

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated. In this case, the counter cation may be an alkali metal or ammonium. Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.

Although not limited to the following, preferred specific examples include C.I. I. Solvent Black 3, 7, 27, 29 and 34; C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2,11,25,35,38,67 and 70; I. Solvent Green 3 and 7; I. Solvent orange 2; and the like.
Particularly preferred among these are: Nubian Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue chemistry 2606e B2 (Manufactured by Co., Ltd.), Aizen Spiron Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, and Neo42 Cy FF4012.
In the present invention, the oil-soluble dye may be used alone or in combination of several kinds.

Moreover, when using an oil-soluble dye as a colorant, other water-soluble dyes, disperse dyes, pigments, and other colorants may be used in combination as long as the effects of the present invention are not impaired.
In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent. Preferable specific examples of the disperse dye include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1,177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse Violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 , 257, 266, 267, 287, 354, 358, 365 and 368; I. Disperse Green 6: 1 and 9;

  It is preferable that the colorant that can be used in the present invention is moderately dispersed in the colored ink composition after being added to the colored ink composition. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.

The colorant may be added directly with each component in the preparation of the color ink composition. However, in order to improve dispersibility, the colorant is added in advance to a dispersion medium such as a solvent or a polymerizable compound, and uniformly dispersed or dissolved. Then, it can be blended.
In the present invention, in order to avoid the deterioration of the solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the colorant contains a polymerizable compound. It is preferable to add and mix in advance in such a dispersion medium. In consideration of only dispersibility, it is preferable to select a monomer having the lowest viscosity as the polymerizable compound used for the addition of the colorant.

  These colorants may be used by appropriately selecting one kind or two or more kinds according to the purpose of use of the colored ink composition.

When using a colorant such as a pigment that remains solid in the colored ink composition, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0.01. It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so that the thickness is ˜0.45 μm, more preferably 0.015 to 0.4 μm. This particle size control is preferable because clogging of the head nozzle can be suppressed and ink storage stability, ink transparency, and curing sensitivity can be maintained.
The content of the colorant in the colored ink composition is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by weight with respect to the total weight of the colored ink composition.

<Other ingredients>
[Tackifying resin]
As another additive, a tackifying resin can be added. Examples of tackifying resins include known (meth) acrylic copolymer resins, rosin ester resins, polymerized rosin resins, disproportionated rosin resins, aliphatic (C5) petroleum resins, aromatic resins ( C9) petroleum resin, aliphatic (C9 hydrogenated) petroleum resin, aliphatic (DCPD) petroleum resin, coumarone-indene resin, hydrogenated terpene resin, terpene phenol resin, styrene resin, substituted styrene resin Phenol resin, maleic acid resin, acid-modified polyolefin resin, ionomer resin, ethylene-acrylic acid copolymer resin, and the like.
The glass transition temperature of the tackifying resin is preferably 25 ° C. or lower, more preferably 0 ° C. to −70 ° C.

  Among these, (meth) acrylic copolymers include (meth) acrylic acid ester polymers, copolymers or other monomers such as (meth) acrylic acid, styrene, vinyltoluene, acrylamide, N- Examples include copolymers with various comonomers such as methylol (meth) acrylamide, glycidyl (meth) acrylate, and 2-hydroxylethyl (meth) acrylate, and in particular, (meth) acrylic copolymers having a Tg of 25 ° C. or less. It is preferable that As these polymers, those produced by known production methods such as solution polymerization and suspension polymerization can be used.

  As the above (meth) acrylic acid ester ("(meth) acrylic acid" means both acrylic acid and methacrylic acid), (meth) acrylic acid methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, t-butyl, hexyl, 2-heptyl, 2-ethylhexyl, 2-ethylbutyl, dodecyl, isobutyl, isodecyl, lauryl, hexadecyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-ethoxyethyl, 2- Examples thereof include dimethylaminoethyl, 2-t-butylaminoethyl, isobornyl or chrysidyl ester.

In order to set the glass transition point to 25 ° C. or lower, for example, 2-ethylhexyl methacrylate, n-butyl methacrylate, acrylic acid, 2-hydroxyethyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid, acrylic Examples thereof include a copolymer and a polymer in which t-butyl acid, stearyl methacrylate, ethyl methacrylate, and the like are combined based on the following approximate expression.
1 / Tg = W1 / T1 + W2 / T2 + W3 / T3 +
Tg: Glass transition temperature of copolymer (absolute temperature)
W1, W2, W3 ...:% by weight of a specific monomer in the copolymer composition
T1, T2, T3 ...: Glass transition temperature (absolute temperature) of a single polymer comprising the monomer

  Examples of the (meth) acrylic copolymer having a glass transition point of 25 ° C. or lower include the above glass transition temperatures, such as vinyl acetate-butyl acrylate copolymer, butyl acrylate-styrene copolymer, and the like. Examples include copolymers with other comonomers.

The (meth) acrylic copolymer has a glass transition temperature of 25 ° C. or lower, preferably 0 ° C. to −70 ° C., and a weight average molecular weight of 5,000 to 100,000. A glass transition temperature of 25 ° C. or lower is preferable because sufficient adhesive strength can be obtained. It is preferable for the weight average molecular weight to be in the above range since sufficient adhesive strength can be obtained.
In addition, a weight average molecular weight converts into a polystyrene molecular weight standard by gel permeation chromatography (GPC), and shows the measured value.

[Dispersant]
It is preferable to add a dispersant when dispersing the colorant. The type of the dispersant is not particularly limited, but a polymer dispersant is preferably used.
Dispersor BYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-164D, DisperBYK-164D, , DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA5080, EFKA5504, EFKA5504, EFKA5504, 62, polymer dispersing agents such as EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse) 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. (Abyssia); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ( Manufactured by Denka Co., Ltd.) and ISONET S-20 (manufactured by Sanyo Chemical Co., Ltd.) “Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polyvalent carboxylic acid)” # 7004 (polyether ester type) ”.
In addition, pigment derivatives such as a phthalocyanine derivative (trade name: EFKA-745 (manufactured by Efka)), Solsperse 5000, 12000, Solsperse 22000 (manufactured by Avicia) can also be used.

  In the present invention, the content of the dispersant in the colored ink composition is appropriately selected depending on the purpose of use, but is preferably 0.01 to 5% by weight based on the weight of the entire colored ink composition.

[Surfactant]
In the present invention, it is preferable to add a surfactant to the ink composition in order to impart stable ejection properties for a long time.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. Further, an organic fluoro compound or a polysiloxane compound may be used as the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826. The polysiloxane compound is preferably a modified polysiloxane compound in which an organic group is introduced into part of the methyl group of dimethylpolysiloxane. Examples of modification include polyether modification, methylstyrene modification, alcohol modification, alkyl modification, aralkyl modification, fatty acid ester modification, epoxy modification, amine modification, amino modification, mercapto modification, etc. is not. These modification methods may be used in combination. Of these, polyether-modified polysiloxane compounds are preferred from the viewpoint of improving ejection stability in inkjet. Examples of the polyether-modified polysiloxane compound include, for example, SILWET L-7604, SILWET L-7607N, SILWET FZ-2104, SILWET FZ-2161 (manufactured by Nippon Unicar Co., Ltd.), BYK-306, BYK-307, BYK- 331, BYK-333, BYK-347, BYK-348, etc. (manufactured by Big Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945 , KF-640, KF-642, KF-643, KF-6020, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (Shin-Etsu Chemical Co., Ltd.) Manufactured).
In the present invention, the content of the surfactant in the ink composition is appropriately selected depending on the purpose of use, but is generally 0.0001 to 1% by weight with respect to the weight of the entire ink composition. preferable. Moreover, these surfactants may be contained alone or in combination of two or more kinds of surfactants.

  Examples of other components include sensitizing dyes, co-sensitizers, other polymerizable compounds, other polymerization initiators, ultraviolet absorbers, antioxidants, antifading agents, conductive salts, solvents, and polymer compounds. And basic compounds.

[Sensitizing dye]
In the present invention, a sensitizing dye may be added to the ink composition in order to absorb specific actinic radiation and promote decomposition of the polymerization initiator. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with the polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizing dye include compounds represented by the following formulas (IX) to (XIII).

In the formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in Formula (IX).

In the formula (XI), A ₂ represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with adjacent A ₂ and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S—, —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ^4, and adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

In the formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or ═NR ⁶⁷ . R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

Preferable specific examples of the compounds represented by formulas (IX) to (XIII) include (E-1) to (E-20) shown below.
In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.

  In the present invention, the content of the sensitizing dye in the ink composition is appropriately selected depending on the purpose of use, but in general, it is 0.05 to 4% by weight with respect to the total weight of the ink composition. preferable.

[Co-sensitizer]
In the present invention, the ink composition preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye to actinic radiation or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of such a co-sensitizer include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethyl phosphite, etc.), Si-- described in JP-A-8-54735 H, Ge-H compound, etc. are mentioned.
In the present invention, the content of the co-sensitizer in the ink composition is appropriately selected depending on the purpose of use, but is preferably 0.05 to 4% by weight based on the weight of the entire ink composition.

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in US Pat. No. 24239, stilbene-based and benzoxazole-based compounds that absorb ultraviolet rays and emit fluorescence, so-called fluorescent brighteners.
The addition amount is appropriately selected according to the purpose, but is preferably 0.5 to 15% by weight in terms of solid content.

〔Antioxidant〕
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

[Anti-fading agent]
In the present invention, various organic and metal complex anti-fading agents can be used in the ink composition. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex-based antifading agent include nickel complexes and zinc complexes. No. 17643, Nos. VII to I, J. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

[Conductive salts]
In the present invention, conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition for the purpose of controlling ejection properties.

〔solvent〕
In the present invention, it is also effective to add a trace amount of an organic solvent to the ink composition in order to improve the adhesion to the support.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include ether solvents.
In this case, it is effective to add the solvent within the range that does not cause the problem of solvent resistance and VOC, and the amount is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight based on the whole ink composition. % Range.

[Basic compounds]
The basic compound is preferably added from the viewpoint of improving the storage stability of the ink composition. As the basic compound that can be used in the present invention, known basic compounds can be used. For example, basic inorganic compounds such as inorganic salts, and basic organic compounds such as amines can be preferably used. .

In addition to this, as necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polyolefin, PET, etc., to improve adhesion to a support such as polyolefin, do not inhibit polymerization A tackifier or the like can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifier resin having a polymerizable unsaturated bond.

<Ink physical properties>
In the present invention, it is preferable to use an ink composition having a viscosity at 25 ° C. of 40 mPa · s or less in consideration of ejection properties. More preferably, it is 5-40 mPa * s, More preferably, it is 7-30 mPa * s. Moreover, it is preferable that the viscosity in discharge temperature (Preferably 25-80 degreeC, More preferably, 25-50 degreeC) is 3-15 mPa * s, More preferably, it is 3-13 mPa * s. It is preferable that the composition ratio of the ink composition is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, ink penetration into the support can be avoided and uncured monomer can be reduced even when a porous support is used. Furthermore, it is preferable that ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.

  In the present invention, the surface tension of the ink composition at 25 ° C. is preferably 20 to 35 mN / m. More preferably, it is 23-33 mN / m. When recording on various supports such as polyolefin, PET, coated paper, and uncoated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 35 mN / m or less.

(Method for producing adhesive tape or adhesive sheet)
The method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention comprises (a) a step of forming a colored image by discharging a radiation-curable colored ink composition on a support, and (b) the discharged ink composition. Irradiating the object with radiation.
That is, the method for producing the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention uses an inkjet recording method to discharge a colored ink composition onto a support to form a colored image, which is irradiated with radiation, preferably ultraviolet rays. Harden.
The method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention includes the steps (a) and (b), whereby an image is formed from the ink composition cured on the support.

Further, in the present invention, the method further includes a step of discharging a radiation-curable colorless ink composition to a region of the support on which a colored image is not formed, and a step of irradiating the discharged colorless ink composition with radiation. It is preferable.
The discharge of the colorless ink composition can be performed simultaneously with the colored ink composition, or the colorless ink composition can be discharged after the discharge of the colored ink composition. Further, before discharging the colored ink composition onto the support, the colorless ink composition can be discharged in advance to a region where the colored ink composition is not discharged.
The discharged colorless ink composition can be irradiated with radiation simultaneously with the irradiation of the colored ink composition. Further, when the discharge of the colored ink composition is before the discharge of the colorless ink composition onto the support, the colorless ink composition is irradiated with radiation after the colored ink composition is cured by irradiation. It can also be done.

  In the step (a) in the method for producing the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention, an ink jet recording apparatus described in detail below can be used. Further, in the colorless ink composition ejection step, the same method as in the step (a) can be employed.

<Inkjet recording apparatus>
There is no restriction | limiting in particular as an inkjet recording device used for this invention, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, any known inkjet recording apparatus including a commercially available product can discharge ink onto the support in the step (a) in the present invention.
Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, an original tank containing an ink composition, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head preferably has a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 × 320 to 4,000 × 4,000 dpi, more preferably 400 × 400 to 1,600 ×. It can be driven so that it can discharge at a resolution of 1,600 dpi, more preferably 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.

  As described above, since it is desirable that the radiation curable ink has a constant temperature for the ejected ink, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

Using the above-described ink jet recording apparatus, the ink composition is ejected by heating the ink composition to preferably 25 to 80 ° C., more preferably 25 to 50 ° C., thereby increasing the viscosity of the ink composition, preferably 3 It is preferable to carry out after lowering to ˜15 mPa · s, more preferably 3 to 13 mPa · s. In particular, it is preferable to use an ink composition having an ink viscosity of 50 mPa · s or less at 25 ° C. because it can be discharged satisfactorily. By using this method, high ejection stability can be realized.
A radiation curable ink composition such as the ink composition used in the present invention generally has a higher viscosity than water-based inks that are usually used in ink jet recording inks, and therefore has a large viscosity fluctuation due to temperature fluctuations during ejection. The ink viscosity fluctuation has a great influence on the change of the droplet size and the change of the droplet discharge speed, and causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink at the time of ejection as constant as possible. Therefore, in the present invention, the control range of the ink temperature is preferably set to ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and further preferably set to ± 1 ° C.

Next, the step (b) of irradiating the discharged colored ink composition with radiation will be described. The colored ink composition is cured when irradiated with radiation. Moreover, the process similar to the process (b) is employable as the process of irradiating the discharged colorless ink composition with radiation.
The ink composition discharged on the support is cured by irradiation with actinic radiation. This is because the polymerization initiator contained in the ink composition is decomposed by irradiation with actinic radiation to generate starting species such as radicals, acids and bases, and the polymerization reaction of the polymerizable compound occurs in the function of the starting species. Because it is promoted. At this time, if a sensitizing dye is present together with the polymerization initiator in the ink composition, the sensitizing dye in the system absorbs actinic radiation to be in an excited state, and promotes decomposition of the polymerization initiator by contacting with the polymerization initiator. And a more sensitive curing reaction can be achieved.

  Here, α rays, γ rays, electron beams, X rays, ultraviolet rays, visible light, infrared rays, or the like can be used as the active radiation used. Although the peak wavelength of actinic radiation is based also on the absorption characteristic of a sensitizing dye, it is preferable that it is 200-600 nm, for example, it is more preferable that it is 300-450 nm, and it is further more preferable that it is 350-420 nm.

In the present invention, the polymerization initiation system of the ink composition has sufficient sensitivity even with a low output actinic radiation. Therefore, it is appropriate to cure the exposed surface with an illuminance of 10 to 4,000 mW / cm ² , more preferably 20 to 2,500 mW / cm ² .

Mercury lamps and gas / solid lasers are mainly used as radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing ultraviolet light curable ink jet recording inks. . However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jets.
Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 350 to 420 nm.
Incidentally, it is preferable that maximum illuminance of LED support on is 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, particularly preferably 50 to 800 mW / cm ² It is.

In the present invention, the ink composition is suitably irradiated with such actinic radiation for 0.01 to 120 seconds, more preferably for 0.1 to 90 seconds.
The irradiation conditions and basic irradiation method of actinic radiation are performed by providing a light source behind the head arranged as described in Japanese Patent Laid-Open No. 2002-316420 and moving the medium by a so-called line method. Is preferred. This method makes it possible to form a color image at high speed, and further increase the speed by arranging a plurality of head units having a plurality of nozzle rows.
Further, as described in JP-A-63-160849, the nozzles are arranged by a width equal to or greater than the width of the image, so-called line heads are provided, and a light source is provided on the rear side of the line heads. By moving and irradiating the medium simultaneously with the droplet, it is possible to form an image at a high speed.
Further, it is possible to irradiate by scanning the head unit and the light source by providing light sources on both sides of the head unit by a so-called shuttle system.
Irradiation with actinic radiation takes a certain period of time (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, still more preferably 0.01 to 0.15 seconds) after ink landing. Will be done. In this way, by controlling the time from ink landing to irradiation to an extremely short time, it is possible to prevent the ink that has landed on the support recording medium from spreading before being cured. In addition, since it can be exposed to the porous support recording medium before the ink penetrates to a deep portion where the light source does not reach, it is preferable because residual unreacted monomer can be suppressed.
Further, the curing may be completed by another light source that is not driven. WO99 / 54415 pamphlet discloses a method using an optical fiber or a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side of the head unit as an irradiation method. The curing method can also be applied to the method for producing the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention.

By adopting the ink jet recording method as described above, the dot diameter of the landed ink can be kept constant even on various supports having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. By superimposing the inks in the order of low lightness, it becomes easier for the irradiation line to reach the lower ink, and good curing sensitivity, reduction of residual monomers, and improvement in adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.
In this way, the ink composition can form an image on the surface of the support by being cured with high sensitivity by irradiation with actinic radiation.

In the method for producing the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention, an image is formed on a support by an ink jet printer, and an adhesive image layer is formed by irradiating ultraviolet rays.
Therefore, it is desirable that the image is formed by forming a reverse image on the transparent support and viewing from the opposite side of the adhesive image layer.
Furthermore, a colored image is formed using a colored ink composition containing a colorant, and a colorant is not contained in a region of the support where no colored image is formed, and a polymerizable compound and a photopolymerization initiator are contained. The colorless ink composition is preferably drawn on a support by an ink jet printer. This is preferable because an adhesive layer can be formed on the entire surface, and a constant adhesive layer can be formed regardless of the image area. It is more preferable to draw an ink composition containing a white colorant on the image or the entire surface because the contrast of the image can be increased.

  Further, it is preferable to further include a step of superimposing the second support having a peelable layer after the step of forming an image by discharging the colored ink composition and before the step of irradiating with radiation. This is preferable because the influence of ultraviolet curing due to oxygen can be suppressed and a more uniform adhesive layer can be formed.

<Support>
As the support used in the present invention, a transparent support is preferable, and a plastic film is preferable. Examples of the plastic film include polyester films such as polyethylene terephthalate, polyethylene naphthalate, and modified polyester, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyvinyl chloride films, polycarbonate films, and the like. Is preferred.

<Peelable layer>
A support having a peelable layer can be prepared by applying a release agent on the above support. As the release agent, one having a dynamic friction coefficient in the range of 0.20 to 0.50 is preferable, and any release agent such as silicone resin, fluororesin, higher fatty acid, soap, wax, animal and vegetable oils can be used. . Any silicone resin in the release sheet industry can be used. Specific examples of such release agents include SD-7239, BY24-162, LTC-300B, LTC-350A manufactured by Toray Dow Corning Silicone Co., Ltd. BY14-403, BY14-405, BY14-407, BY14-413, BY14-414, BY-14-411, BY14-420, and KS-845, KS-770, KNS- manufactured by Shin-Etsu Chemical Co., Ltd. 202A, KNS-305, KNS-316, KNS-319, KNS-320, X-62-1232, X-62-1233, and the like. The coating amount of the coating is the release agent is 0.4 to 2.0 g / m ² C., particularly 0.6~1.3g / m ² is preferred.

  The pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet obtained according to the present invention can impart decorativeness with a colored image to an arbitrary article by forming an image on a transparent support and affixing the image to an arbitrary article or the like.

  Moreover, it can use also for the use which forms an image on both surfaces of a support body, and affixes the articles | goods using this. When a transparent plate is bonded using an adhesive tape or an adhesive sheet having a colored image formed on both sides, the colored image can be observed from both sides of the transparent plate.

  Moreover, the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet obtained by the method for producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention can also be used as a hydraulic transfer film in a hydraulic pressure transfer method. The hydraulic transfer method is a means for forming a printed pattern layer by a transfer method mainly on a three-dimensional surface or curved surface due to unevenness, and is liquid-soluble or liquid-swelled having a printed pattern layer (also referred to as a transfer layer) on the surface. After floating the hydraulic transfer film made of a conductive film on the liquid surface with the printed pattern layer on the hydraulic transfer film as the upper surface, by pressing various molded bodies that are the transfer body from above, This is a method of transferring a printed pattern layer to the surface of a molded body using hydraulic pressure. Japanese Patent Publication No. 52-41683 and Japanese Patent Publication No. 54-33115 can be referred to for the hydraulic transfer system.

In this case, a support having liquid solubility or liquid swellability is selected. Having liquid solubility or liquid swellability means having a property of absorbing or dissolving or swelling and spreading. The liquid is preferably water, and the support preferably has water solubility or water swellability. At the time of hydraulic transfer, the support is dissolved or attached to the transfer target and can perform hydraulic transfer.
As a support material used for hydraulic transfer, films such as polyvinyl alcohol (PVA) resin, polyvinyl pyrrolidone, acetyl cellulose, polyacrylamide, acetyl butyl cellulose, gelatin, glue, sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose can be used. . Among these, a polyvinyl alcohol resin film is preferable because it is excellent in solubility in water and is easily available. The thickness of the support used can be appropriately selected depending on the purpose, but is preferably 10 μm or more and 200 μm or less. It is more preferably 50 μm or more and 200 μm or less, and further preferably 70 μm or more and 170 μm or less. It is preferable for the thickness of the support to be in the above range since it is excellent in liquid solubility and liquid swellability.

The hydraulic transfer method generally includes (1) a step of bringing a film for hydraulic transfer into contact with a liquid with the support side down, (2) a step of activating the transfer layer with an activator, and (3) activation. A step of transferring the transferred layer to a transfer target, and (4) a step of removing the support.
In the present invention, since the sticky image is formed on the support, the step of activating with the activator can be omitted.
In addition, since the transfer layer formed on the surface of the transfer object has viscosity, a surface protective layer is provided so as to overcoat the transfer layer of the transfer object after the step of removing the support. Is preferred.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following description, “parts” means “parts by weight” unless otherwise specified.

The radical polymerization ink materials used in the present invention are as shown below.
(Pigment)
・ IRGALITE BLUE GLVO (Cyan pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335 D (Magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (Black pigment, manufactured by Ciba Specialty Chemicals)
・ Taipeku CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)

(Polymerizable compound)
2-ethylhexyl acrylate (Tg: -85 ° C, manufactured by Aldrich)
Light acrylate IO-A (Tg: -83 ° C, isooctyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.)
N-vinylcaprolactam (Tg: 148 ° C., NVC, manufactured by ISP)
Sartomer SR9003 (Tg: 32 ° C., propoxylated neopentyl glycol diacrylate, manufactured by Sartomer)
NK ester AMP-10G (Tg: 5 ° C., phenoxyethyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

(Photopolymerization initiator)
・ Lucirin TPO (photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), manufactured by BASF)
・ Benzophenone (photopolymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.)
Irgacure 184 (photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone), manufactured by Ciba Specialty Chemicals)

(Dispersant)
-Solsperse 32000 (dispersant, manufactured by Noveon)
-Solsperse 36000 (dispersant, manufactured by Noveon)
(Other)
・ First cure ST-1 (polymerization inhibitor, manufactured by Chem First)
・ BYK 307 (surfactant, manufactured by BYK Chemie)

The cationic polymerization ink material used in the present invention is as shown below.
(Pigment)
・ IRGALITE BLUE GLVO (Cyan pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335 D (Magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (Black pigment, manufactured by Ciba Specialty Chemicals)
・ Taipeku CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)

(Polymerizable compound)
・ Denacol EX-121 (Tg: −60 ° C., 2-ethylhexyl glycidyl ether, manufactured by Nagase Sangyo Co., Ltd.)
・ Cyracure UVR6105 (Tg: 170 ° C., manufactured by Dow Chemical)

OXT-221 (Tg: 50 ° C., bis (3-ethyl-3-oxetanyl) ether, manufactured by Toagosei Co., Ltd.)

(Photopolymerization initiator)
・ CPI-100P (sulfonium salt, manufactured by San Apro)

・ Dibutoxyanthracene (manufactured by Kawasaki Chemical Industry Co., Ltd.)

(Dispersant)
・ Solsperse 32000 (Noveon)
-Solsperse 36000 (Noveon)
(Surfactant)
・ BYK 307 (manufactured by BYK Chemie)

(Measurement of glass transition temperature)
About the polymeric compound, the glass transition temperature (Tg) was calculated | required with the following methods. When the polymerizable compound is a radical polymerizable compound, 86.5 parts of the aforementioned radical polymerizable compound and photopolymerization initiation (Lucirin TPO 8.5 parts, benzophenone 3.0 parts, Irgacure 184 2.0 parts) are mixed. The polymer was prepared by coating with a bar coater to a film thickness of 100 μm and curing with a metal halide lamp.
When the polymerizable compound is a cationic polymerizable compound, 87.0 parts of the cationic polymerizable compound and a photopolymerization initiator (CPI-100P 12.0 parts, dibutoxyanthracene 1.0 part) are mixed, A polymer was prepared by the above method.
5 mg of the obtained polymer was sampled, and the glass transition temperature was measured on the sampled polymer sample (sample) using a differential scanning calorimetry apparatus (Differential Scanning Calorimetry, DSC).

(Preparation of pigment mill base for radical polymerizable ink composition)
Hereinafter, a pigment mill base for a radical polymerizable ink composition was prepared.
<Preparation of cyan mill base A>
300 parts by weight of IRGALITE BLUE GLVO, 600 parts by weight of Sartomer SR9003, and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain cyan mill base A. Cyan mill base A was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of magenta mill base B>
300 parts by weight of CINQUASIA MAGENTA RT-335 D, 600 parts by weight of Sartomer SR9003, and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain magenta mill base B. The magenta mill base B was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of yellow mill base C>
300 parts by weight of NOVOPERM YELLOW H2G, 600 parts by weight of Sartomer SR9003, and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain Yellow Mill Base C. The yellow mill base C was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of Black Mill Base D>
300 parts by weight of SPECIAL BLACK 250, 600 parts by weight of Sartomer SR9003, and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain a black mill base D. The black mill base D was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 7 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of white mill base E>
A white mill base E was obtained by stirring and mixing 500 parts by weight of Typek CR60-2, 450 parts by weight of NK ester AMP-10G, and 50 parts by weight of Solsperse 36000. The white mill base E was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of pigment mill base for cationic polymerizable ink composition)
Hereinafter, a pigment mill base for a cationic polymerizable ink composition was prepared.
<Preparation of cyan mill base F>
300 parts by weight of IRGALITE BLUE GLVO, 600 parts by weight of OXT-221 and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain cyan mill base F. Cyan mill base F was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of magenta mill base G>
CINQUASIA MAGENTA RT-335 D (300 parts by weight), OXT-221 (600 parts by weight) and Solsperse 32000 (100 parts by weight) were stirred and mixed to obtain magenta mill base G. The magenta mill base G was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of yellow mill base H>
300 parts by weight of NOVOPERM YELLOW H2G, 600 parts by weight of OXT-221, and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain yellow mill base H. The yellow mill base H was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of Black Mill Base I>
300 parts by weight of SPECIAL BLACK 250, 600 parts by weight of OXT-221 and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain Black Mill Base I. The black mill base I was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed using a zirconia bead having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 5 hours and 30 minutes.

<Preparation of white mill base J>
A white mill base J was obtained by stirring and mixing 500 parts by weight of Tyco CR60-2, 450 parts by weight of OXT-221 and 50 parts by weight of Solsperse 36000. The white mill base J was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of radical polymerizable ink composition (radical ink))
<Preparation of radical ink 1>
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink.
[Cyan ink composition]
Cyan mill base A 6.0 parts N-vinyl caprolactam 5.0 parts 2-ethylhexyl acrylate 45.4 parts Light acrylate IO-A 25.0 parts First cure ST-1 0.05 part Luciferin TPO 8 .5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ BYK 307 0.05 parts ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate) Copolymer, glass transition temperature -20 ° C, weight average molecular weight 50,000) 5 parts

<Preparation of radical ink 2>
The following components were stirred with a high-speed water-cooled stirrer to obtain a magenta UV inkjet ink.
[Magenta ink composition]
-Magenta mill base B 12.0 parts-N-vinylcaprolactam 5.0 parts-2-ethylhexyl acrylate 42.4 parts-Light acrylate IO-A 22.0 parts-First cure ST-1 0.05 parts-Lucirin TPO 8 .5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ BYK 307 0.05 parts ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate) Copolymer, glass transition temperature -20 ° C, weight average molecular weight 50,000) 5 parts

<Preparation of radical ink 3>
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink.
[Yellow color ink composition]
・ Yellow mill base C 12.0 parts ・ N-vinylcaprolactam 5.0 parts ・ 2-ethylhexyl acrylate 42.4 parts ・ Light acrylate IO-A 22.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8 .5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ BYK 307 0.05 parts ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate) Copolymer, glass transition temperature -20 ° C, weight average molecular weight 50,000) 5 parts

<Preparation of radical ink 4>
The following components were stirred with a high-speed water-cooled stirrer to obtain a black UV inkjet ink.
[Black ink composition]
Black mill base D 6.0 parts N-vinylcaprolactam 5.0 parts 2-ethylhexyl acrylate 45.4 parts Light acrylate IO-A 25.0 parts First cure ST-1 0.05 part Lucirin TPO 8 .5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ BYK 307 0.05 parts ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate) Copolymer, glass transition temperature -20 ° C, weight average molecular weight 50,000) 5 parts

<Preparation of radical ink 5>
The following components were stirred with a high-speed water-cooled stirrer to obtain a white UV inkjet ink.
[White color ink composition]
・ White mill base E 31.0 parts ・ N-vinylcaprolactam 5.0 parts ・ 2-ethylhexyl acrylate 33.4 parts ・ Light acrylate IO-A 12.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8 .5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ BYK 307 0.05 parts ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate) Copolymer, glass transition temperature -20 ° C, weight average molecular weight 50,000) 5 parts

<Preparation of radical ink 6>
The following components were stirred with a high-speed water-cooled stirrer to obtain a colorless UV inkjet ink.
[Colorless ink composition]
・ N-vinylcaprolactam 5.0 parts ・ 2-ethylhexyl acrylate 48.4 parts ・ Light acrylate IO-A 28.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8.5 parts ・ Benzophenone 3.0 Parts Irgacure 184 2.0 parts BYK 307 0.05 parts Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature -20 ° C, weight average molecular weight 50,000) 5 parts

(Preparation of cationic polymerizable ink composition (cationic ink))
<Preparation of cationic ink 1>
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink.
[Cyan ink composition]
・ Cyan Mill Base F 6.0 parts ・ Denacol EX-121 56.0 parts ・ UVR6105 19.9 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ BYK 307 0.1 part ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ° C., weight average molecular weight 50,000) 5 parts

<Preparation of cationic ink 2>
The following components were stirred with a high-speed water-cooled stirrer to obtain a magenta UV inkjet ink.
[Magenta ink composition]
-Magenta mill base G 12.0 parts-Denacol EX-121 53.0 parts-UVR6105 16.9 parts-CPI-100P 12.0 parts-Dibutoxyanthracene 1.0 part-BYK 307 0.1 part-Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ° C., weight average molecular weight 50,000) 5 parts

<Preparation of cationic ink 3>
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink.
[Yellow color ink composition]
・ Yellow Mill Base H 12.0 parts ・ Denacol EX-121 53.0 parts ・ UVR6105 16.9 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ BYK 307 0.1 part ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ° C., weight average molecular weight 50,000) 5 parts

<Preparation of cationic ink 4>
The following components were stirred with a high-speed water-cooled stirrer to obtain a black UV inkjet ink.
[Black ink composition]
・ Black Mill Base I 6.0 parts ・ Denacol EX-121 56.0 parts ・ UVR6105 19.9 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ BYK 307 0.1 part ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ° C., weight average molecular weight 50,000) 5 parts

<Preparation of cationic ink 5>
The following components were stirred with a high-speed water-cooled stirrer to obtain a white UV inkjet ink.
[White color ink composition]
・ White mill base J 30.0 parts ・ Denacol EX-121 35.0 parts ・ UVR6105 17.9 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ BYK 307 0.1 part ・ Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ° C., weight average molecular weight 50,000) 5 parts

<Preparation of cationic ink 6>
The following components were stirred with a high-speed water-cooled stirrer to obtain a colorless UV inkjet ink.
[Colorless ink composition]
・ Denacol EX-121 50.0 parts ・ UVR6105 32.9 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ BYK 307 0.1 part ・ Acrylic resin a (2-ethylhexyl methacrylate / methacrylic acid) N-butyl acid / butyl acrylate / methacrylic acid 2-hydroxylethyl copolymer, glass transition temperature-20 ° C., weight average molecular weight 50,000) 5 parts

(Example 1-1)
<Inkjet image recording method>
Recording on a support was performed using an inkjet recording experimental apparatus having six piezo-type inkjet nozzles. The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV light was condensed to an exposure surface illuminance of 2,100 mW / cm ² , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landing on the support. Further, the integrated light amount irradiated to the image was set to 6,000 mJ / cm ² . As an ultraviolet lamp, a HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) was used. In the present invention, dpi represents the number of dots per 2.54 cm.
By using the above method, the cyan, magenta, yellow and black inks of the radical ink are used on an A4 size support (HK-31WF film pressure 188 μm, PET, manufactured by Higashiyama Film Co., Ltd.) so that the average film pressure of the cured film is 12 μm. Thus, a color image printed matter 1 was produced. An image having an area of 25% with respect to the entire surface of the support was produced.

(Example 1-2)
The same image as the color image print 1 was prepared in the same manner, and an adhesive layer was formed using a radical colorless ink in a region having no image (75% of the entire support) to prepare a color image print 2.

(Example 1-3)
The same image as the color image printed matter 1 was produced in the same manner, and a white solid printing was performed on the entire surface of the image portion with an average film pressure of a cured film of 12 μm using radical white ink, thereby producing a color image printed matter 3.

(Examples 1-4 to 1-6)
Also, a color image printed matter 4 was prepared using cyan, magenta, yellow, and black inks of the cationic ink (Example 1-4).
The same image as the color image print 4 was prepared in the same manner, and an adhesive layer was formed using a cationic colorless ink in a region without an image (75% of the entire support) to prepare a color image print 5 (Example 1- 5).
The same image as the color image printed matter 4 was produced in the same manner, and a white solid printing was performed on the entire surface of the image portion with an average film pressure of a cured film of 12 μm using a cationic white ink, thereby producing a color image printed matter 6 (Example 1-6). .

(Example 2)
A release layer in which a release agent (Shin-Etsu Chemical KNS-316) was applied to the above support by a bar coater so as to be 1.0 g / m ² was prepared, and when the color image printed matter 1 was prepared, UV irradiation was stopped, and a color image was obtained. After drawing with an inkjet, the support body which apply | coated the peeling layer was bonded together, and UV light was irradiated after that, and the adhesive seal | sticker 1 was produced.

(Comparative Example 1)
Except for changing 2-ethylhexyl acrylate and light acrylate IO-A to Sartomer SR9003 and NK ester AMP-10G, respectively, cyan, magenta, yellow, black, white and colorless inks were used in the same manner as radical inks 1-6. Produced. Next, a color image print 7 was prepared in the same manner as the color image print 2.

(Comparative Example 2)
Using the ink composition prepared in Comparative Example 1, a support coated with a release layer was bonded in the same manner as in Example 2, and irradiated with UV light to prepare an adhesive seal 2.

(Comparative Example 3)
Except that Denacol EX-121 was changed to OXT-221 (Tg: 50 ° C. di (1-ethyl (3-oxetanyl)) methyl ether manufactured by Toagosei Co., Ltd.) Cyan, magenta, yellow, black, white and colorless inks were prepared. Next, a color image print 8 was produced in the same manner as the color image print 5.

  The results are shown in the table below.

The following evaluation was performed on the support (printed material) on which an image was formed, which was obtained in Examples and Comparative Examples.
(Adhesion evaluation method)
The printed materials 1 to 7 were cut into a width of 50 mm, and the peak peel strength was measured with a peel tester (Duplo PT-200) using a test piece that was pressed and bonded to a stainless steel support at room temperature.
The adhesive seal (Example 2) was evaluated in the same manner after peeling from the release layer. Note that the adhesive seal 2 (Comparative Example 2) did not function as an adhesive seal without adhering to the release layer.

(Evaluation of image contrast)
The image pasted on the stainless steel was visually evaluated.
The evaluation criteria are as follows.
○: Good.
Δ: The color appears light and the underlying color is reflected.

(Examples 3 to 8)
The ink prepared in Example 1 and the ink prepared in Comparative Example 1 were mixed at the ratio shown in Table 4 to prepare ink sets of Examples 3-8. Using the ink set, cyan, magenta, yellow, black, white and colorless inks were produced in the same manner as radical inks 1-6. Next, similarly to the color image print 2, color image prints 9 to 14 were produced.
The peel strength was measured for the obtained color image printed matter.

Claims (5)

A step of forming a colored image by discharging a radiation curable colored ink composition on a support; and
Irradiating the discharged ink composition with radiation,
The colored ink composition contains a colorant, a polymerizable compound, and a photopolymerization initiator,
A method for producing a pressure-sensitive adhesive tape or a pressure-sensitive adhesive sheet, wherein a glass transition temperature of a cured film of a polymerizable compound alone contained in a colored ink composition is 25 ° C. or lower. A step of discharging a radiation-curable colorless ink composition to a region of the support on which a colored image is not formed, and
Further comprising irradiating the discharged colorless ink composition with radiation,
The colorless ink composition contains a polymerizable compound and a photopolymerization initiator, and does not contain a colorant.
The manufacturing method of the adhesive tape or adhesive sheet of Claim 1.   The manufacturing method of the adhesive tape or adhesive sheet of Claim 2 whose glass transition temperature of the cured film only with the polymeric compound contained in the said colorless ink composition is 25 degrees C or less.   The manufacturing method of the adhesive tape or adhesive sheet of any one of Claims 1-3 whose said support body is a transparent support body.   5. The method according to claim 1, further comprising a step of overlaying the second support having a peelable layer after the step of discharging the colored ink composition and forming the image and before the step of irradiating with radiation. The manufacturing method of the adhesive tape or adhesive sheet as described in one.