JP4866705B2 - Manufacturing method of printed matter - Google Patents

Description

The present invention relates to the production how the printed material to which the adhesive is coated to adhere by applying pressure.

  In recent years, procedures and processes using information have become common with the progress of the information society. Among them, there are many cases where information used for procedures and processing is illegally or accidentally acquired and misused.

  For this reason, it is required to avoid inadvertent distribution of information.For example, in a postcard for notifying information, it is composed of a plurality of postcard pieces that are foldable and the information on the postcard pieces is printed. What is folded so that it may oppose and these are adhere | attached so that peeling is possible is used. The adhesive used for this postcard is bonded by pressurization, and the postcard can be peeled and adhered by folding and pressing the postcard after coating and before drying.

  However, in postcards as described above, the adhesive was applied because the postcard pieces were peeled and adhered by folding and pressing after the adhesive was applied and before the adhesive dried. When stored in a state, blocking occurs due to an adhesive that is not dried, and therefore, there is a problem that it cannot be wound and stored. Further, when folded in this state, the adhesive is not dried, and thus there is a problem that the folded portion is folded.

The present invention has been made in view of the problems of the conventional techniques as described above, and can be wound and stored without blocking in a state where the adhesive is applied, and can be folded. uneven folding the folding portion is never occur when it is intended to provide a printed matter manufacturing how.

In order to achieve the above object, the present invention provides:
On the sheet base material, a printed layer is formed, and a method for producing a printed material having an adhesive surface that is adhered to each other by being superimposed and pressed,
Forming the printed layer on the sheet substrate;
A step of applying a radiation curable adhesive that adheres by applying pressure to the entire surface of the sticking surface of the sheet substrate on which the printing layer is formed;
Curing the radiation curable adhesive applied to the sheet substrate;
Winding the sheet base material coated with the radiation curable adhesive in a state where nothing is stuck to the sheet base material ;
A step of pulling out the wound sheet base material from the wound state when used as the printed matter ;
Folding and pressurizing the drawn sheet base material so that the sticking surfaces face each other.

  In the present invention configured as described above, a print layer is formed on the first sheet base material, and the sheet base materials on which the print layer is formed are bonded to each other by being superimposed and pressed. The adhesive was applied to the entire surface of the sticking surface by applying a radiation curable adhesive that was bonded by applying pressure, and after curing the radiation curable adhesive, the sheet substrate was wound up. Even when wound and stored in a state, blocking does not occur. Thereafter, the wound sheet base material is pulled out from the wound state, and the sheet base material is folded and pressed so that the sticking surfaces face each other. At this time, since the radiation curable adhesive is in a cured state, the folding portion does not fold.

In addition, a printed layer is formed on a sheet base material, and a printed material having a sticking surface that is adhered to each other by being overlapped and pressed,
Forming a first printed layer on the sheet substrate;
Applying a radiation curable adhesive that adheres by applying pressure to the entire surface of the sticking surface of the sheet substrate on which the first printing layer is formed;
Curing the radiation curable adhesive applied to the sheet substrate;
Winding the sheet base material coated with the radiation curable adhesive in a state where nothing is stuck to the sheet base material ;
A step of pulling out the wound sheet base material from the wound state when used as the printed matter ;
Forming a second printed layer on the sticking surface of the drawn sheet base material.

  In the present invention configured as described above, the first printed layer is formed on the first sheet base material, and among the sheet base materials on which the first printed layer is formed, they are superimposed on each other and pressed. Applying a radiation curable adhesive that adheres by applying pressure to the entire surface of the bonding surface to be adhered, and after curing the radiation curable adhesive, the sheet substrate is wound up, Even when the agent is wound and stored in a coated state, blocking does not occur. Then, the wound sheet base material is pulled out from the wound state, and a second printed layer is formed on the sticking surface of the sheet base material.

  As described above, in the present invention, the first printed layer is formed on the sheet substrate, and the sheet substrates on which the first printed layer is formed are bonded to each other by being superimposed on each other and pressed. Since a radiation curable adhesive that adheres by applying pressure is applied to the entire surface of the pasting surface to be cured, and the radiation curable adhesive is cured, the sheet substrate is wound up. In the processed state, the sheet can be wound and stored without causing blocking, and thereafter, when the sheet base material is pulled out from the wound state and folded, the folding portion does not occur.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 1 is a diagram showing a configuration example of an information concealing postcard as an embodiment of a printed matter of the present invention, (a) is a diagram showing one side of a spread state, and (b) is the other side of the spread state. The figure which shows a surface, (c) is AA 'sectional drawing shown to (a). 2 is a diagram showing a state in which the information concealing postcard 1 shown in FIG. 1 is folded. FIG. 2A is a view seen from the first paper piece 2 side, and FIG. 2B is a third paper piece 4. The figure seen from the side, (c) is an AA ′ cross-sectional view shown in (a).

  In this embodiment, as shown in FIG. 1, the first paper piece part 2, the second paper piece part 3 and the third paper piece part 4 are connected via the folding parts 5a and 5b, and can be folded at the folding parts 5a and 5b. It is configured.

  The first paper piece 2 is formed by applying a radiation curable adhesive which is cured by irradiating radiation onto one surface of a base sheet 11 made of coated paper or the like serving as a base substrate. The layer 13a is laminated, and the destination information 2a is printed thereon, whereby the individual print layer 14a as the second print layer is formed. On the other surface of the base sheet 11, a preprint layer 12b as a first print layer is formed by printing preprint information 3c and the like, and a radiation curable adhesive is applied on the entire surface thereof. As a result, the adhesive layer 13b is laminated, and the notification information 3d is printed thereon, whereby the individual print layer 14b as the second print layer is formed.

  The second paper piece portion 3 is formed with a preprint layer 12a as a first print layer by printing preprint information 3a or the like on one surface of the base sheet 11, and a radiation curable adhesive thereon. Is applied to the entire surface, thereby laminating an adhesive layer 13a and further printing the detailed information 3b thereon to form an individual print layer 14a. A preprint layer 12b is formed on the other surface of the base sheet 11 by printing the preprint information 3c and the like, and a radiation curable adhesive is applied on the entire surface of the preprint layer 12b. And the notification information 3d is printed thereon to form the individual print layer 14b.

  The third paper piece portion 4 has a preprint layer 12a formed on one surface of the base sheet 11 by printing the preprint information 3a and the like, and a radiation curable adhesive is coated on the entire surface. As a result, the adhesive layer 13a is laminated, and the detailed information 3b is printed thereon, whereby the individual print layer 14a is formed. On the other surface of the base sheet 11, the pre-print layer 12b is formed by printing the advertisement information 4a, and the adhesive layer 13b is laminated on the entire surface by applying a radiation curable adhesive thereon. Has been.

  Here, the radiation curable adhesive constituting the adhesive layers 13a and 13b will be described in detail.

  The radiation curable adhesive constituting the adhesive layers 13a and 13b uses an aqueous emulsion containing natural rubber fine particles.

  Natural rubber-based fine particles are fine particles of natural rubber-based rubber and the like, and are the main components that develop an adhesive force by pressure bonding, and natural rubber-based rubber has an isoprene skeleton, which is the main component of natural rubber, Similarly, natural rubber is not particularly limited as long as it has self-adhesiveness.

  However, in order to improve the dispersibility and compatibility of the natural rubber fine particles with respect to the radiation curable first acrylic compound as a medium, the natural rubber fine particles are preferably a copolymer of natural rubber rubber and an acrylic monomer. .

  Examples of acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, lauryl (meth) acrylate-tridecyl, tridecyl (meth) acrylate, cetyl (meth) acrylate -(Meth) acrylic acid esters such as stearyl, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and phenyl methacrylate; (meth) acrylic acid amide and methylol (meth) acrylic acid (Meth) acrylic acid amides such as amide; Acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, butyl (meth) acrylate Reactive acrylic monomers such as aminoethyl, glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate; ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, tri (meth) acrylate tri Ethylene glycol, di (meth) acrylic acid tetraethylene glycol, di (meth) acrylic acid decaethylene glycol, di (meth) acrylic acid pentadecaethylene glycol, di (meth) acrylic acid pentacontactor ethylene glycol, di (me ) Crosslinkable acrylic monomers such as butylene acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and diethylene glycol di (meth) acrylate phthalate These can be used, and two or more of these can be used in combination.

  In addition to improving the dispersibility of the natural rubber-based fine particles, in order to improve the fixability of the adhesive composition to the substrate, the natural rubber-based fine particles include a co-polymer of natural rubber rubber and styrene monomer. Polymers are preferred.

  Styrene monomers include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, chlorostyrene, bromostyrene, etc. These can be used, and two or more of these can be used in combination.

  From the above viewpoint, a natural rubber rubber, a copolymer of an acrylic monomer and a styrene monomer may be used as the natural rubber fine particles. Further, if necessary, two or more kinds of natural rubber fine particles can be used in combination.

  On the other hand, the radiation-curable first acrylic compound is not particularly limited, but an oligomer having at least one acryloyl group or methacryloyl group is preferable from the viewpoint of realizing good performance of the adhesive composition and the pressure-sensitive adhesive layer. Further, (an oligomer having two or more acryloyl groups or methacryloyl groups is more preferable. Further, in addition to these (meth) acryloyl groups, an oligomer having a radical reactive unsaturated group at the same time can also be used. Examples of saturated groups include allyl groups and methallyl groups.

  The type of oligomer is not particularly limited, but the weight average molecular weight is preferably 30 to 1000, such as oligoethylene glycol, epoxy resin oligomer, polyester resin oligomer, polyamide resin oligomer, urethane resin oligomer, oligovinyl alcohol, phenol resin oligomer, etc. Is used.

  Specific examples of the radiation curable first acrylic compound as described above include oligoethylene glycol di (meth) acrylate, nonylphenol EO modified (n = 4) acrylate, epoxy resin oligomer acrylate ester (for example, diester of bisphenol A). Glycidyl ether diacrylate), reaction product of epoxy resin oligomer, acrylic acid and methyltetrahydrophthalic anhydride, reaction product of epoxy resin oligomer and 2-hydroxyethyl acrylate, diglycidyl ether and diallylamine of epoxy resin oligomer Reaction product of glycidyl diacrylate and phthalic anhydride ring-opening copolymer, methacrylic acid dimer and polyol ester, polyester obtained from acrylic acid, phthalic anhydride and propylene oxide , Reaction product of oligoethylene glycol, maleic anhydride and glycidyl methacrylate, reaction product of oligovinyl alcohol and N-methylol acrylamide, esterified oligo vinyl alcohol with succinic anhydride and glycidyl methacrylate added , Oligomer obtained by reacting dialmyl ester of pyromellitic dianhydride with p, p'-diaminodiphenyl, reaction product of ethylene-maleic anhydride copolymer and allylamine, methyl vinyl ether-maleic anhydride copolymer Reaction product of polymer and 2-hydroxyethyl acrylate, further reacted with glycidyl methacrylate, oligooxyalkylene segment and / or saturated oligoester segment via urethane bond Ligated, urethane oligomer having an acryloyl group or a methacryloyl group at both ends, can be mentioned a terminal acrylic-modified isoprene rubber or butadiene rubber, among others, oligoethylene glycol di (meth) acrylate are preferable.

  Moreover, a photopolymerizable monomer can also be used as a radiation curable 1st acrylic compound as needed. Preferred photopolymerizable monomers include (meth) acrylic acid, (meth) acrylic acid esters such as alkyl, cycloalkyl, alkyl halide, alkoxyalkyl, hydroxyalkyl, aminoalkyl, tetrahydrofurfuryl, allyl, glycidyl, benzyl, Phenoxy acrylate, phenoxy methacrylate, alkylene glycol, mono or diacrylate and methacrylate of polyoxyalkylene glycol, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, acrylamide, methacrylamide or derivatives thereof such as alkyl groups Acrylamide, methacrylamide and diacetone mono- or di-substituted with hydroxyalkyl groups Acrylamide and methacrylamide, N, can be mentioned N'- alkylene-bis acrylamide and methacrylamide and the like.

  In particular, in the case of applications where curing shrinkage is an obstacle, for example, isobornyl acrylate or methacrylate, norbornyl acrylate or methacrylate, dicyclopentenoxyethyl acrylate or methacrylate, dicyclopentenoxypropyl acrylate or methacrylate Diethylene glycol dicyclopentenyl monoether acrylic ester or methacrylic ester, oligooxyethylene or oligopropylene glycol dicyclopentenyl mono ether acrylic ester or methacrylic ester, dicyclopentenyl cinnamate, dicyclopentenoxy 3,9-bis (1,1-bismethyl-2-oxy) such as ethyl cinnamate, dicyclopentenoxyethyl monofumarate or difumarate Ethyl) -spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9- Mono- and diacrylates such as bis (2-oxyethyl) -spiro [5,5] undecane and 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane Or mono-, dimethacrylate, or mono-, diacrylate, or mono-, dimethacrylate, or the methyl ether of these monoacrylates or methacrylates, 1-azabicyclo [2,2,2] -3-octenyl acrylate or methacrylate, bicyclo [2,2,1 Such as 5-heptene-2,3-dicarboxyl monoallyl ester, dicyclopentadienyl acrylate or methacrylate, dicyclopentadienyl oxyethyl acrylate or methacrylate, a dihydrodicyclopentadienyl acrylate or methacrylate is used.

  Moreover, a polyfunctional acrylic compound can also be used as a radiation-curable 1st acrylic compound as needed. As the polyfunctional acrylic compound, (meth) acrylic ester of copolymerizable α, β-unsaturated polyvalent carboxylic acid, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, dimethacrylic acid 1, Dimethacrylic acid alkylene glycol esters such as 4-butylene glycol and propylene glycol dimethacrylate, trimethylolpropane EO-added triacrylate, and the like can be used.

  The ratio of the radiation-curable first acrylic compound as described above to 100 parts by mass of the natural rubber fine particles is preferably 50 parts by mass or more and more preferably 80 parts by mass or more from the viewpoint of the performance of the obtained adhesive layers 13a and 13b. Preferably, 100 parts by mass or more is more preferable, while 500 parts by mass or less is preferable, 300 parts by mass or less is more preferable, and 200 parts by mass or less is still more preferable. In addition, as needed, 2 or more types of radiation-curable 1st acrylic compounds can also be used together, and it is preferable in this case that the total amount of a radiation-curable 1st acrylic compound exists in said range.

  Depending on the type of radiation-curable first acrylic compound used, a polymerization initiator is used in combination. Examples of the polymerization initiator include benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin-isopropyl ether, benzoin alkyl ethers such as benzoin isobutyl-ether, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, Examples include benzyl, diacetyl, diphenyl sulfide, eosin, thionine, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, and methylbenzoylformate. These polymerization initiators may be used alone or in combination of two or more. The usage-amount is 0.1-30 mass parts with respect to 100 mass parts of total amounts of an acrylic compound.

  A method for preparing an adhesive composition using the natural rubber fine particles and the radiation curable first acrylic compound as described above will be described.

  First, an aqueous emulsion containing 40-80% by mass of natural rubber-based fine particles is added to the radiation curable first acrylic compound.

  This is mixed and the mixture is heated using, for example, a warm bath. By heating, water as a medium of the water-based emulsion is vaporized and gradually removed out of the mixture. As the water decreases, the dispersion medium of the radiation curable first acrylic compound is replaced with the radiation curable first acrylic compound from water.

  When this method is actually performed, the viscosity of the mixture increases as the water decreases, and when the dispersion medium is replaced, the viscosity of the mixture rapidly decreases. Such a sudden change in viscosity is considered to be caused by a phase transition. By adopting this method, the natural rubber fine particles are sufficiently dispersed without causing aggregation of the natural rubber fine particles. An agent composition can be obtained.

  In addition to the dispersibility of the natural rubber-based fine particles, natural rubber-based fine particles having an average particle size desirable from the viewpoint of the performance of the obtained adhesive composition and adhesive layer can be realized. The average particle diameter of the natural rubber fine particles is preferably 0.01 μm or more, more preferably 0.03 μm or more, further preferably 0.05 μm or more, on the other hand, 5 μm or less, more preferably 1 μm or less, 0 More preferably, it is 5 μm or less. The average particle diameter is measured on the basis of weight using a light scattering method or the like.

  In addition, when the above-described method is employed, the dispersion medium can be directly replaced without removing water as a medium from the natural rubber-based fine particle-containing aqueous emulsion or drying the natural rubber-based fine particles. As a result, the moisture content of the resulting adhesive composition can be sufficiently reduced, specifically 10 mass% or less, more preferably 5 mass% or less, and even more preferably 1 mass% or less.

  In order to obtain an adhesive composition in which natural rubber fine particles having a desired average particle diameter are sufficiently uniformly dispersed and the water content is sufficiently low, an aqueous emulsion containing natural rubber fine particles and a radiation-curable first acrylic compound are used. Careful selection of the mixing ratio is required. Specifically, the ratio of the radiation-curable first acrylic compound to 100 parts by mass of the natural rubber-based fine particle-containing aqueous emulsion is preferably 25 parts by mass or more, more preferably 40 parts by mass or more, and 50 parts by mass or more. Is more preferably 250 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less.

  Further, in order to obtain an adhesive composition in which natural rubber fine particles having a desired average particle diameter are sufficiently uniformly dispersed and the water content is sufficiently low, the temperature at which water in the natural rubber fine particle-containing aqueous emulsion is vaporized is carefully selected. Must be selected. Specifically, 20 ° C. or higher is preferable, 30 ° C. or higher is more preferable, 40 ° C. or higher is further preferable, while 70 ° C. or lower is preferable, 60 ° C. or lower is more preferable, and 50 ° C. or lower is even more preferable.

  Further, in order to obtain an adhesive composition with sufficiently uniform distribution of natural rubber fine particles having a desired average particle size and a sufficiently low water content, the water content of the aqueous emulsion containing natural rubber fine particles can be increased. Careful selection of vaporization method is required. Specifically, the vaporized water is forcibly removed by blowing warm air or reducing the pressure, and the replacement of the dispersion medium is completed in about 30 minutes to 5 hours.

  When a copolymer of natural rubber rubber and at least one of an acrylic monomer and a styrene monomer is used as the natural rubber fine particles, the copolymer is synthesized prior to replacement of the above dispersion medium.

  In such a copolymer, at least one of an acrylic monomer and a styrene monomer is added to a natural rubber emulsion, and at least one of the acrylic monomer and the styrene monomer is vinyl polymerized in the natural rubber emulsion. Can be synthesized.

  In this case, the reaction ratio between the natural rubber fine particles and the acrylic monomer and styrene monomer is in the range of 1 to 80 parts by mass of the acrylic monomer and styrene monomer with respect to 100 parts by mass of the natural rubber fine particles, As the polymerization initiator, for example, organic peroxides can be used, and redox initiators composed of organic peroxides and ethylenediamines are preferable. Among them, t-butyl hydroperoxide (t-BHPO) and tetraethylene are preferable. A redox initiator composed of pentaamine (TEPA) is preferred. Further, as the organic peroxide, ketone peroxide, diacyl peroxide, dialkyl peroxide, peroxy ketal, peroxy ester, peroxy carbonate and the like are preferable, and ethylene diamines include ethylene diamine (EDA) and diethylene triamine (DETA). Tetraethylenetetraamine (TETA), pentaethylenehexamine (PEHA) and the like are preferable.

  Moreover, the usage-amount of a polymerization initiator shall be the range of 0.01-10 mass parts with respect to 100 mass parts of natural rubber-type fine particles.

  Furthermore, as required, terpene resin, rosin, oil-soluble phenol resin, coumarone indene resin, petroleum hydrocarbon resin, terpene resin derivative, rosin derivative, oil-soluble phenol resin derivative, coumarone indene resin derivative It is also possible to add a tackifier such as a derivative of a petroleum hydrocarbon resin.

  The emulsion immediately after synthesis of the copolymer obtained as described above contains unreacted monomers and the like in addition to the copolymer, but radiation is not added to the emulsion immediately after synthesis without purifying the copolymer. A curable first acrylic compound can be mixed to replace the dispersion medium.

  Furthermore, after replacing the dispersion medium, a second acrylic compound is added as necessary. By using the second acrylic compound in combination, the applicability of the adhesive composition can be controlled in a wider range, the adhesive layer obtained can have a higher adhesive force, and the adhesive layer and the substrate can be more bonded to each other. Strength can be realized.

  From such a viewpoint, the second acrylic compound is preferably an acrylic monomer, an acrylic oligomer having a polymerization degree of 2 to 10, or a mixture thereof, more specifically, an acrylic type. Oligomers obtained by vinyl polymerization of monomers are preferred, and acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Hexyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, lauryl (tri) acrylate (tri) (Meth) acrylic acid tridecyl, (meth) acrylic acid cetyl-stearyl, (meth) acrylic acid (Meth) acrylic esters such as stearyl lurate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and phenyl methacrylate; (meth) such as (meth) acrylic acid amide and (meth) acrylic acid methylolamide Acrylic amides; (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate Reactive acrylic monomers such as ethyl, butylaminoethyl (meth) acrylate, glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate; ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate , Di (meta) a Triethylene glycol laurate, tetraethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, pentacontactor ethylene glycol di (meth) acrylate Crosslinkable acrylic monomers such as butylene (meth) acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and diethylene glycol di (meth) acrylate phthalate Etc. are preferable. These monomers can be used in combination of two or more as required, and a mixture of oligomers having different degrees of polymerization can also be used.

  Furthermore, a radiation-curable first acrylic compound can be used as the second acrylic compound. In this case, it is also possible to use those obtained by replacing the oligomer component of the radiation-curable first acrylic compound with a monomer component, such as paracumylphenol EO-modified (n = 1) acrylate.

  Moreover, the addition amount of the second acrylic compound is carefully set in consideration of the performance of the obtained adhesive composition and the adhesive layer, and is 1 part by mass or more with respect to 100 parts by mass of the radiation curable first acrylic compound. Is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 10 parts by mass or less.

  After replacing the dispersion medium as described above, a polymerization initiator for curing the radiation curable first acrylic compound is required when forming the adhesive layer after adding the second acrylic compound as necessary. Add further if necessary.

  Moreover, a styrene-butadiene rubber latex may be added from a viewpoint of improving the adhesive strength of the obtained adhesive layer and the fixability of the adhesive layer to the substrate. Styrene-butadiene rubber latex is considered to improve the adhesion between the substrate to which the adhesive composition is applied and the natural rubber-based fine particles.

  Styrene-butadiene rubber latex is mainly composed of styrene-butadiene rubber (SBR), and as SBR, emulsion polymerization SBR such as SBR driver and SBR latex; solution polymerization SBR such as random SBR, block SBR and symmetric block SBR is used. be able to.

  Further, the characteristics of SBR greatly depend on the copolymerization ratio of styrene and butadiene. From such a viewpoint, the styrene content is low (30% by mass or less), the styrene content is medium (more than 30% by mass and 70% by mass or less), and the styrene content is high (over 70% by mass). ) Etc. are carefully selected and used in styrene-butadiene rubber latex.

  Examples of the SBR used as the main component of the styrene-butadiene rubber latex include a non-modified type, a vinylpyridine-modified type, and a carboxy-modified type. Among these, carboxy-modified styrene-butadiene rubber latex is preferable because it has excellent adhesion to the substrate and can sufficiently improve the adhesion between the natural rubber-based fine particles and the substrate.

  As a mixing ratio of the natural rubber fine particles and the styrene-butadiene rubber latex, in order to sufficiently improve the adhesive force of the natural rubber fine particles, 1 part by mass of the styrene-butadiene rubber latex with respect to 100 parts by mass of the natural rubber fine particles. The content is preferably set to the above, and more preferably 5 parts by mass or more. On the other hand, in order not to impair other characteristics of the natural rubber-based fine particles, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.

  In addition, by setting the content of the styrene-butadiene rubber latex to an appropriate value, sufficient interaction between the obtained adhesive layer and the printing agent such as ink and toner can be realized. Can be realized. Furthermore, since the adhesive strength after pressure bonding the adhesive layer can be moderated, it is possible to suppress the peeling of the adhesive layer when it is unnecessary after the pressure bonding, and the adhesive layer can be easily used when desired after pressure bonding. Can be peeled off.

  Furthermore, in order to realize sufficient blocking resistance of the resulting pressure-sensitive adhesive composition, it is preferable to add a filler having a non-affinity to the natural rubber-based fine particles to the adhesive composition. Since the surface of the adhesive layer (adhesion surface) is formed with the addition of the filler, it is considered that the adhesion surface is prevented from adhering to other surfaces prior to pressure bonding of the adhesion surface, and the blocking resistance is improved. .

  In addition, if irregularities are formed on the surfaces (adhesive surfaces) of the adhesive layers 13a and 13b by adding a filler, the adhesion between the adhesive surfaces proceeds after the bonding of the adhesive surfaces, and the adhesive force increases. Can also be suppressed. As a result, when it is necessary to peel the adhesive surface after the adhesive surface is pressure-bonded, the adhesive surface can be easily peeled off.

  Moreover, when it is necessary to prevent the transparency of the adhesive layers 13a and 13b from being hindered, it is preferable that the filler has a regular particle shape. Examples of such materials include various silica-based fillers, various starch-based fillers, synthetic zeolite, microspherical (meth) acrylic resin, microspherical polyethylene, spherical alumina, glass powder, shirasu balloon, activated clay, titanium oxide. And zinc oxide. These fillers may be used alone or in combination of two or more.

  In addition, the average particle diameter of these fillers is preferably 0.01 μm or more, more preferably 1 μm or more, and on the other hand, 35 μm or less is preferable, and 25 μm or less is more preferable. Further, when two or more kinds having different particle diameters are used in combination, the surfaces of the adhesive layers 13a and 13b can be easily formed in a concavo-convex shape, which is advantageous in improving blocking resistance and peeling performance.

  Among the fillers as described above, silica-based fillers and starch-based fillers are preferable because of their low affinity with natural rubber-based fine particles and sufficient blocking resistance.

  As a compounding amount of the filler, in the case of a silica-based filler, it is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, with respect to 100 parts by mass of the natural rubber-based fine particles, 100 mass parts or less are preferable, 80 mass parts or less are more preferable, and 60 mass parts or less are still more preferable.

  In the case of starch-based fillers, 10 parts by mass or more is preferable, 100 parts by mass or more is more preferable, 30 parts by mass or more is more preferable, and 200 parts by mass or less is preferable. 180 parts by mass or less, more preferably 160 parts by mass or less.

  In addition to the additives as described above, an ultraviolet absorber (ultraviolet absorber) may be added to the adhesive composition in order to improve ultraviolet resistance.

  Examples of such UV absorbers include salicylic acids such as phenyl salicylate, butylphenyl salicylate and octylphenyl salicylate; dihydroxybenzophenone, hydroxymethoxybenzophenone, hydroxyoctoxybenzophenone, hydroxydodecyloxybenzophenone, hydroxymethoxysulfobenzophenone and bis (methoxyhydroxy). Benzophenones such as benzoylphenyl) methane; (hydroxymethylphenyl) benzotriazole, (hydroxybutylphenyl) benzotriazole, (hydroxydibutylphenyl) benzotriazole, (hydroxybutylmethylphenyl) chlorobenzotriazole, (hydroxydibutylphenyl) chlorobenzo Triazole, (hydroxydiamilfe It can be exemplified hindered amine and the like; le) benzotriazole and [hydroxy (tetrahydrophthalimide) methyl phenyl] benzotriazole such as benzotriazole; cyanoacrylates such as ethyl hexyl cyano-diphenyl acrylate and ethyl cyano diphenylacrylate.

  Moreover, antioxidant may be required. Antioxidants include amines including aromatic secondary amines such as amine-ketones, diphenylamines, diaryl-P-phenylenediamines, and alkylaryl-P-phenylenediamines; monophenols, bisphenols And phenols containing hydroquinone; organic sulfur; phosphites; composites of these can be used, and among these, phenols are preferred because of less contamination and coloring.

  Furthermore, if necessary, an adhesive composition can be prepared by using a synthetic rubber emulsion in combination. Synthetic rubber emulsions include emulsions in which synthetic rubbers such as polyisoprene rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, chloroprene rubber, butyl rubber, polyurethane rubber, thiocol rubber and acrylic rubber are dispersed in an aqueous solvent. It can be illustrated.

  Moreover, a pressure-sensitive adhesive composition can also be produced using a synthetic resin emulsion in combination. Examples of synthetic resin emulsions include polyvinyl acetate emulsions, vinyl acetate-ethylene copolymer emulsions, polyacrylate emulsions, and polyvinyl chloride emulsions. Among these synthetic resin emulsions, those having a glass transition temperature (Tg) of −30 to 20 ° C. are suitable.

  In addition, an emulsifier can be added to stabilize the dispersion of the natural rubber fine particles. As such an emulsifier, anionic or nonionic surfactants such as rosin soap, naphthalene sulfonate, fatty acid soap and alkylbenzene sulfonate are used.

  Furthermore, a pH adjuster, an antioxidant, a tackifier, a viscosity adjuster, an anti-aging agent, a stabilizer, a colorant and the like can be mixed with the adhesive composition as necessary.

  In order to produce the radiation curable adhesive constituting the adhesive layers 13a and 13b shown in FIG. 1, an aqueous emulsion containing the natural rubber fine particles as described above is added to 100 parts by mass of the natural rubber fine particles. 70 parts by mass of polyethylene glycol diacrylate (trade name: Aronix M-240, manufactured by Toagosei Co., Ltd.) and trimethylolpropane EO-added triacrylate (trade name: Biscote # 360, manufactured by Osaka Organic Chemical Co., Ltd.) After thoroughly stirring 30 parts by mass, the dispersion medium was replaced in 1 hour by raising the temperature of the mixture to 50 ° C. and removing the water vaporized under reduced pressure. The mass ratio of the aqueous emulsion containing natural rubber fine particles to the mixture of polyethylene glycol diacrylate and trimethylolpropane EO-added triacrylate was 160: 100.

  To this was added 4 parts by mass of a photopolymerization initiator (trade name: BYCURE 55, manufactured by Akzo Nobel) to obtain an ultraviolet curable pressure-sensitive adhesive composition.

  It was 0.5 mass% when the moisture content of the obtained pressure-sensitive-adhesive composition was measured. The natural rubber fine particles had an average particle size of 0.2 μm and a uniform dispersibility.

  As shown in FIG. 2, the information hiding postcard 1 configured as described above is folded at the folding portions 5a and 5b, and the adhesive layer 14b of the first paper piece portion 2 and the second paper piece portion 3 is laminated thereon. And the first paper piece part 2 and the second paper piece part 3 are detachably bonded by the adhesive layer 14b, and the adhesive layer 14a of the second paper piece part 3 and the third paper piece part 4 The second paper piece 3 and the third paper piece 4 are detachably bonded by the adhesive layer 14a. As a result, the detailed information 3b printed from the second paper piece portion 3 to the third paper piece portion 4 becomes invisible from the outside, and is printed from the first paper piece portion 2 to the second paper piece portion 3. The notification information 3d thus made becomes invisible from the outside.

  Below, the manufacturing method of the information hiding postcard 1 comprised as mentioned above is demonstrated.

  First, the process of manufacturing the information hiding postcard 1 to a storage state shape will be described.

  FIG. 3 is a diagram showing a configuration example of a manufacturing apparatus for manufacturing the information concealment postcard 1 shown in FIG. 1, and shows a configuration of a part for manufacturing the information concealment postcard 1 to a storage state shape. 4 is a flowchart for explaining a method of manufacturing the information hiding postcard 1 using the manufacturing apparatus shown in FIG. 3, and FIG. 5 is a method of manufacturing the information hiding postcard 1 shown in FIG. FIG.

  As shown in FIG. 3, the manufacturing apparatus of this example includes a pre-printing unit 21, an adhesive coating unit 22, and an adhesive curing unit 23 provided in the conveyance path of the postcard sheet 1 a wound up in a roll shape. Have.

  After the base sheet 11 is rolled up in a continuous form, the postcard sheet 1a is pulled out. First, the pre-printing unit 21 prints the pre-print information 3a and 3c and the advertisement information 4 on both sides of the base sheet 11, respectively. As a result, as shown in FIG. 5A, pre-printed layers 12a and 12b are formed (step S1). The pre-print information 3a and 3c and the advertisement information 4 are common regardless of the destination of the information concealment postcard 1, and the base sheet 11 is repeated on the postcard sheet 1a in which the base sheet 11 is continuous. Printed.

Next, by applying an adhesive having the above-described composition on the entire front and back surfaces of the base sheet 11 on which the preprinted layers 12a and 12b are formed in the preprinting unit 21 in the adhesive coating unit 22. As shown in FIG. 5B, the adhesive layers 13a and 13b are stacked (step S2). Specifically, the pressure sensitive adhesive composition as described above is applied to the base sheet 11 by offset printing so as to be 6 g / m ² . At this time, when coated paper is used as the base sheet 11, the adhesive is repelled by the resin on the surface and by the preprinted layers 12a and 12b, and the adhesive layers 13a and 13b are formed on the surface of the base sheet 11. Although fine unevenness is formed, in this application, including that state, it is defined as coating on the entire surface.

  Next, in the adhesive curing unit 23, the adhesive layers 13a and 13b laminated on the base sheet 11 are irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the adhesive layers 13a and 13b ( Step S3).

  Thereafter, the postcard sheet 1a is wound up and stored as a sheet roll 1b (step S4). At this time, since the postcard sheet 1a is wound after the adhesive layers 13a and 13b are cured, it can be wound and stored without blocking in a state where the adhesive is applied.

  Next, a method of processing from the information concealment postcard 1 in the storage state to the state shown in FIG. 2 will be described.

  FIG. 6 is a diagram showing a configuration example of a manufacturing apparatus for manufacturing the information hiding postcard 1 shown in FIG. 1, and a configuration for processing from the information hiding postcard 1 in the storage state to the state shown in FIG. Show. FIG. 7 is a flowchart for explaining a method of manufacturing the information hiding postcard 1 using the manufacturing apparatus shown in FIG. 6, and FIG. 8 is a method of manufacturing the information hiding postcard 1 shown in FIG. FIG.

  As shown in FIG. 6, the manufacturing apparatus of this example is provided with a variable printing unit 31, a cutting unit 32, and a folding / crimping unit 33 provided in the conveyance path of the postcard sheet 1a wound as a sheet roll 1b. And have.

  The postcard sheet 1a wound up in a roll shape as the sheet roll 1b is pulled out (step S11). First, in the variable printing unit 31, the destination information 2a is formed on the surface on which the adhesive layers 13a and 13b of the base sheet 11 are laminated. By printing the detailed information 3b and the notification information 3d, the individual print layers 14a and 14b are formed as shown in FIG. 8A (step S12). The destination information 2a, the detailed information 3b, and the notification information 3d are different depending on the destination of the information concealment postcard 1, and are individually printed for each base sheet 11 on the postcard sheet 1a in which the base sheet 11 is continuous. The

  Next, the cutting section 32 cuts the postcard sheet 1a that has become continuous into a single piece for each base sheet 11 as shown in FIG. 8B (step S13).

  After that, the folding / crimping section 33 folds the information hiding postcard 1 in the form of a single piece at the folding sections 5a and 5b as shown in FIG. 8C, and sets the sealing machine to a gap between rollers of 100 μm. Then, the first paper piece 2 and the second paper piece 3 are detachably bonded by the adhesive layer 14b, and the second paper piece 3 and the third paper piece 4 are peeled by the adhesive layer 14a. Bonding is possible (step S14). At this time, since the adhesive layers 13a and 13b are already cured, the folding portions 5a and 5b are not folded.

  In the present embodiment, the postcard sheet 1a wound up in a roll shape as the sheet roll 1b has a destination on the surface where the adhesive layers 13a and 13b of the base sheet 11 are laminated in the variable printing unit 31. The information 2a, the detailed information 3b, and the notification information 3d are respectively printed to form the individual print layers 14a and 14b, and the folding / crimping section 33 folds the information concealment postcard 1 that is a single piece. The first paper piece 2 and the second paper piece 3 are detachably bonded to each other by the adhesive layer 14b, and the second paper piece 3 and the third paper piece 4 are bonded to the adhesive layer 14a. The postcard sheet 1a wound in a roll shape as the sheet roll 1b is pulled out from the wound state, and then the destination information 2a, the detailed information 3b, and the communication By printing the information 3d, the individual print layers 14a and 14b are formed only, or folded at the folding portions 5a and 5b, and the first paper piece 2 and the second paper piece 3 are separated by the adhesive layer 14b. It can also be applied to what is manufactured by simply adhering the second paper piece part 3 and the third paper piece part 4 so as to be peelable by the adhesive layer 14a.

(Other embodiments)
FIG. 9 is a diagram showing a configuration example of a reciprocating postcard as another embodiment of the printed matter of the present invention, (a) is a diagram showing one surface, (b) is a diagram showing the other surface, c) is a cross-sectional view taken along line AA ′ shown in FIG.

  As shown in FIG. 9, the present embodiment is a reciprocating postcard 101 in which an outgoing communication unit 102 and a reply unit 103 are connected via a folding unit 105, and is configured by stacking three base sheets 111 a to 111 c.

  The base sheet 111 a has a shape that extends between the transmission unit 102 and the reply unit 103, and the pre-print layer 112 a is formed by printing the reply destination information 103 a on one surface of the reply unit 103. The pre-print layer 112b is formed by printing the order form column 103b on the other side. Also, the pre-printing layers 112a and 112b are formed by performing pre-printing on both sides of the communication unit 102 as well. Further, in the transmission part 102, adhesive layers 113a and 113b, which are coated with an adhesive having the same composition as that constituting the adhesive layers 13a and 13b shown in FIG. 1, are laminated on both sides.

  The base sheet 111b is laminated on the surface on which the reply destination information 103a is printed by the reply unit 103 of the base sheet 111a in an area excluding the vicinity of the folding part 105 of the area to be the transmission part 102 of the base sheet 111a. . The preprinted layer 112e is formed on the surface not facing the base sheet 111a by printing the notification information 102b, and the preprinted layer 112c is also formed on the surface facing the base sheet 111a. Further, an adhesive layer 113c formed by applying an adhesive having the same composition as that constituting the adhesive layers 113a and 113b is laminated on the pre-printed layer 112c. The adhesive layer 113c and the base sheet are laminated. The base sheet 111b is detachably bonded to the transmission part 102 of the base sheet 111a by the adhesive layer 113a laminated on the 111a. In addition, the end of the base sheet 111b on the side of the folded portion 105 is bonded to the base sheet 111a so as not to be peeled by an adhesive 115a that cannot be peeled.

  The base sheet 111c is laminated on the surface side of the base sheet 111a on which the order sheet field 103b is printed in the area serving as the transmission section 102 of the base sheet 111a. The individual print layer 114 is formed on the surface not facing the base sheet 111a by printing the outgoing address information 102a, and the pre-print layer 112d is formed on the surface facing the base sheet 111a. Further, an adhesive layer 113d obtained by applying an adhesive having the same composition as that constituting the adhesive layers 113a and 113b is laminated on the pre-printed layer 112d, and the adhesive layer 113d and the base sheet are laminated. The base sheet 111c is detachably bonded to the transmission part 102 of the base sheet 111a by the adhesive layer 113b laminated on the 111a. Further, the end of the base sheet 111c on the side of the folded portion 105 is bonded to the base sheet 111a so as not to be peeled off by the non-peelable adhesive 115b.

  In the reciprocating postcard 101 configured as described above, similarly to the information concealment postcard 1 shown in FIG. 1, the adhesive layers 113 a to 113 e are respectively laminated on the continuous sheets in which the base sheets 111 a to 111 c are continuous. Thereafter, the adhesive layers 113a to 113e are cured, and the continuous sheet can be wound into a roll and stored. At this time, as in the present embodiment, it is also conceivable to laminate the adhesive layers 113a to 113e partially or only on one surface of the base sheets 111a to 111c.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the structural example of the information concealment postcard which is one Embodiment of the printed matter of this invention, (a) is a figure which shows one side of a spread state, (b) is a figure which shows the other side of a spread state (C) is AA 'sectional drawing shown to (a). It is a figure which shows the state by which the information concealment postcard shown in FIG. 1 was folded, (a) is the figure seen from the 1st paper piece part side, (b) is the figure seen from the 3rd paper piece part side, (c). FIG. 3 is a cross-sectional view taken along line AA ′ shown in FIG. It is a figure which shows the structural example of the manufacturing apparatus for manufacturing the information concealment postcard shown in FIG. It is a flowchart for demonstrating the manufacturing method of the information concealment postcard using the manufacturing apparatus shown in FIG. It is a lamination figure for demonstrating the manufacturing method of the information concealment postcard shown in FIG. It is a figure which shows the structural example of the manufacturing apparatus for manufacturing the information concealment postcard shown in FIG. It is a flowchart for demonstrating the manufacturing method of the information concealment postcard using the manufacturing apparatus shown in FIG. It is a lamination figure for demonstrating the manufacturing method of the information concealment postcard shown in FIG. It is a figure which shows the structural example of the reciprocating postcard which is other embodiment of the printed matter of this invention, (a) is a figure which shows one surface, (b) is a figure which shows the other surface, (c) is ( It is AA 'sectional drawing shown to a).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Information concealment postcard 1a Postcard sheet 1b Sheet roll 2 First paper piece part 2a Destination information 3 Second paper piece part 3a, 3c Pre-print information 3b Detailed information 3d Notification information 4 Third paper piece part 4a Advertisement information 5a, 5b, 105 Folding part 11, 111a-111c Base sheet 12a, 12b, 112a-112e Pre-print layer 13a, 13b, 113a-113d Adhesive layer 14a, 14b, 114 Individual print layer 21 Pre-print part 22 Adhesive coating part 23 Adhesive curing part 23 31 Variable printing section 32 Cutting section 33 Folding / crimping section 101 Reciprocating postcard 102 Outbound section 102a Outbound destination information 102b Notification information 103 Reply section 103a Reply destination information 103b Purchase order field 115a, 115b Adhesive

Claims (2)

On the sheet base material, a printed layer is formed, and a method for producing a printed material having an adhesive surface that is adhered to each other by being superimposed and pressed,
Forming the printed layer on the sheet substrate;
A step of applying a radiation curable adhesive that adheres by applying pressure to the entire surface of the sticking surface of the sheet substrate on which the printing layer is formed;
Curing the radiation curable adhesive applied to the sheet substrate;
Winding the sheet base material coated with the radiation curable adhesive in a state where nothing is stuck to the sheet base material ;
A step of pulling out the wound sheet base material from the wound state when used as the printed matter ;
A method for producing a printed matter, comprising: folding and pressurizing the drawn sheet base material so that the sticking surfaces face each other. On the sheet base material, a printed layer is formed, and a method for producing a printed material having an adhesive surface that is adhered to each other by being superimposed and pressed,
Forming a first printed layer on the sheet substrate;
Applying a radiation curable adhesive that adheres by applying pressure to the entire surface of the sticking surface of the sheet substrate on which the first printing layer is formed;
Curing the radiation curable adhesive applied to the sheet substrate;
Winding the sheet base material coated with the radiation curable adhesive in a state where nothing is stuck to the sheet base material ;
A step of pulling out the wound sheet base material from the wound state when used as the printed matter ;
Forming a second printed layer on the sticking surface of the drawn sheet base material.

Images