CN101855310B - Composition for forming contact-bonding coating film of actinic-energy-ray curable type and strippable adhesive-coated paper employing the same - Google Patents
Composition for forming contact-bonding coating film of actinic-energy-ray curable type and strippable adhesive-coated paper employing the same Download PDFInfo
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- CN101855310B CN101855310B CN200880115150XA CN200880115150A CN101855310B CN 101855310 B CN101855310 B CN 101855310B CN 200880115150X A CN200880115150X A CN 200880115150XA CN 200880115150 A CN200880115150 A CN 200880115150A CN 101855310 B CN101855310 B CN 101855310B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/005—Repairing damaged coatings
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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Abstract
A composition for forming a contact-bonding coating film of the actinic-energy-ray curable type which comprises a carboxylated acrylic polymer (A), an ingredient curable with actinic energy rays (B), and a photopolymerization initiator (C), the amount of the photopolymerization initiator (C) being 10-30 parts by weight per 100 parts by weight of the actinic-energy-ray-curable ingredient (B). The composition hence has satisfactory applicability and needs no drying step after application to thereby improve processing efficiency. The composition can satisfactorily cure. Through curing, the composition comes to have excellent adhesive force and strippability in stripping. Consequently, a strippable adhesive-coated paper made with this composition combines excellent adhesive force with strippability and is highly practical.
Description
Technical field
The present invention relates to film by the active energy ray curable pressure sensitive adhesion that active energy beam (activated energy ray) solidifies forms with composition (activatedenergy curable composition for PSA coating) and the bonding converted paper of separability (removable adhesive paper) that uses said composition, and wherein said pressure sensitive adhesion is filmed to form with composition and can be passed through pressure (pressure) and separability is bonding.
Background technology
In recent years, the automatization of making for the reduction that realizes postal cost, information typewriting and notice thing etc., postcard (secretconfidential mail) system that replaces sealing letter and have a personal delivery popularizes rapidly.This system is for the content that hides Info, employing will be folding with paper, and will relative paper the mode of (removable) applying strippingly.The adhesive composition that uses in this binding face has various, but all can not fully satisfy waste paper regenerated, the keeping quality, manufacturing cost etc. of gloss, operating efficiency, the paper on surface.
For glossiness, the operating efficiency that improves above-mentioned surface; proposed to use a kind of method of adhesive composition, this adhesive composition will have specified molecular weight and second-order transition temperature (methyl) acrylic copolymer, be selected from ultra-violet solidified monomer (UV-curable monomer) with (methyl) acryl and at least a ultra-violet solidified composition in the oligopolymer and Photoepolymerizationinitiater initiater and cooperate (patent documentation 1,2) that forms.
In addition; also consider to use a kind of adhesive composition; this adhesive composition contains the elastomerics that contains (methyl) acryl of specified molecular weight, ultra-violet solidified composition and Photoepolymerizationinitiater initiater, and above-mentioned three kinds of compositions are set at specifically contain proportional (patent documentation 3).
Patent documentation 1: Japanese kokai publication hei 11-349854
Patent documentation 2: TOHKEMY 2000-136320
Patent documentation 3: TOHKEMY 2004-210879
Summary of the invention
The problem that invention will solve
Yet, as above-mentioned patent documentation 1,2 adhesive composition, form homodisperse state though its composition components is compatible with each other, and coating excellent in stability, but solidified nature (reactivity) existing problems also exist once bending some and float the situation that (abrasion) produces.In addition, the problem that also exists bounding force to become strong along with the process of time.On the other hand, though the adhesive composition of above-mentioned patent documentation 3 has been eliminated the problem of this solidified nature, have excellent solidified nature, and bounding force etc. do not change in time basically and change, coating is inferior, can not obtain stable binding property.
In addition, require the equal excellent adhesive composition of manufacturing price ratio of surface luster, processing efficiency of operation, the converted paper of printing surface on the market.
The present invention In view of the foregoing makes, its purpose is, provide the active energy ray curable pressure sensitive adhesion to film and form the bonding converted paper of separability of using composition and using said composition, described composition can be coated with well, drying process when not needing to be coated with and improved the processing efficiency of operation, and can obtain good curing, the bounding force excellence after the curing, and also the separability when peeling off is also excellent.
For the scheme of dealing with problems
To achieve these goals, first main idea of the present invention is filmed to form for the active energy ray curable pressure sensitive adhesion and is used composition, it contains carboxylic acrylic acid polymer (A), active energy ray-curable composition (B) and Photoepolymerizationinitiater initiater (C), with respect to the above-mentioned active energy ray-curable composition (B) of 100 weight parts, the content of above-mentioned Photoepolymerizationinitiater initiater (C) is 10～30 weight parts.
In addition, second main idea of the present invention is the bonding converted paper of separability, and it is above-mentioned active energy ray curable pressure sensitive adhesion to be filmed to form coat on the paper surface with composition, and obtains with active energy beam curing.
(realizing process of the present invention)
Namely, the inventor etc. are further investigation repeatedly In view of the foregoing, in order to obtain to have the adhesive composition of good coating and solidified nature and separability bounding force excellence, centered by acrylic acid polymer (A), active energy ray-curable composition (B) and Photoepolymerizationinitiater initiater (C) composition, study.Found that, contain carboxyl by making in the aforesaid propylene acid based polymer, and fasten the pass at above-mentioned Photoepolymerizationinitiater initiater and its cure component, above-mentioned Photoepolymerizationinitiater initiater is set at more than ever before specified proportion, the active energy ray curable pressure sensitive adhesion that can obtain to have good coating and solidified nature concurrently and have a good adhesion of separability excellence is filmed to form and is used composition, thereby has finished the present invention.Usually, when excessively increasing above-mentioned Photoepolymerizationinitiater initiater, cured article can become lower molecular weight, therefore, tend to suppress content, yet find, by Photoepolymerizationinitiater initiater being set to such an extent that more known content was more than in the past, and make and contain carboxyl in the acrylic acid polymer, thus, can obtain the adhesive composition that the excellent bonding converted paper of separability is used.
Think that the mechanism that obtains this effect is as described below.Usually, the postcard of the folding of sheet that uses in aforementioned postcard system invades fine silica gel particle bonding on the paper by pressurization mutually, thereby makes paper fit mutually, under the pressure of the degree that applies with hand, silica gel particle can interlock, therefore, can not attach again.In the present invention, can think that by specially using a large amount of Photoepolymerizationinitiater initiaters, the surface after curing produces more small island structure, bring into play the effect of above-mentioned silica gel, thereby shown that good pressurized adhesion and (after peeling off) prevent binding property again.In addition, it is believed that, contain carboxyl in the acrylic acid polymer by making, distance between this carboxyl narrows down to the distance of can interact (hydrogen bond) by pressurization, thereby bounding force is improved, but then, because the steric hindrance of carboxyl is big, can prevent that bounding force is increased to the degree that is difficult to peel off.
The effect of invention
As mentioned above, the present invention films to form for the active energy ray curable pressure sensitive adhesion and uses composition, it contains carboxylic acrylic acid polymer (A), active energy ray-curable composition (B) and Photoepolymerizationinitiater initiater (C), with respect to the above-mentioned active energy ray-curable composition (B) of 100 weight parts (being designated hereinafter simply as " part "), the content of above-mentioned Photoepolymerizationinitiater initiater (C) is 10～30 parts.Therefore, can be coated with well, the drying process when not needing to be coated with can improve the processing efficiency of operation, and can solidify well, the glossiness on the surface after the curing and bounding force excellence, and when peeling off, have good separability.Therefore, use the bonding converted paper of separability of said composition to have excellent bounding force and separability therefrom, and the practicality height.
In addition, the weight-average molecular weight of carboxylic acrylic acid polymer (A) is 100,000 when following, and coating can be more excellent.
The second-order transition temperature of carboxylic acrylic acid polymer (A) is in-60 ℃～20 ℃ scope the time, and it is excellent that the flexibility of gained bonding coat can become.
With respect to 100 parts above-mentioned active energy ray-curable composition (B), containing of carboxylic acrylic acid polymer (A) is proportional when being 5～45 parts, and bounding force can be more excellent.
When active energy ray-curable composition (B) contained following (b1)～(b3), it is more excellent that the separability bounding force can become,
(b1) at least a in epoxy (methyl) acrylate and urethane (methyl) acrylate;
(b2) has the alefinically unsaturated compounds except (b1) of 2 above ethylenically unsaturated groups;
(b3) has the alefinically unsaturated compounds except (b1) of an ethylenically unsaturated group.
All with respect to above-mentioned active energy ray-curable composition (B), (b1)～(b3) to contain proportional be that 5～20 weight %, (b2) they are 40～80 weight %, when (b3) is 10～40 weight %, then can further obtain the balance of bounding force and separability (removability) at (b1).
Embodiment
Then, describe embodiment of the present invention in detail.Yet the present invention is not subjected to the restriction of this embodiment.
Active energy ray curable pressure sensitive adhesion of the present invention is filmed, and to form with composition (followingly abbreviating " pressure sensitive adhesion film (PSA coating) form use composition " sometimes as) be the pressure sensitive adhesion that contains carboxylic acrylic acid polymer (A), active energy ray-curable composition (B) and Photoepolymerizationinitiater initiater (C) the formation composition of filming, with light such as ultraviolet ray, infrared rays, hertzian wave or the curing of electron rays isoreactivity energy-ray such as X ray, gamma-rays.
At first, carboxylic acrylic acid polymer (A) is described.
" carboxylic acrylic acid polymer (A) "
Employed carboxylic acrylic acid polymer (A) forms (methyl) alkyl acrylate (a1), carboxylic monomer (a2) copolymerization among the present invention, as required, can also with other co-polymerized monomer (a3) copolymerization.
In addition; in the present invention; (methyl) vinylformic acid refers to acrylic or methacrylic acid; (methyl) propenyl ((meth) acryl) refers to propenyl (acryl) or methylpropenyl (methacryl); (methyl) acryl ((meth) acryloyl) refers to acryl (acryloyl) or methacryloyl (methacryloyl), and (methyl) acrylate refers to acrylate or methacrylic ester.
As above-mentioned (methyl) alkyl acrylate (a1), for example can list (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-propyl, (methyl) methyl acrylate, (methyl) ethyl propenoate etc.In the middle of these, the carbon number that preferably uses alkyl is (methyl) alkyl acrylate of 1～10, and the carbon number that especially preferably uses alkyl is (methyl) alkyl acrylate of 1～5.In the middle of these, especially preferably use (methyl) ethyl propenoate, (methyl) n-butyl acrylate.These (methyl) alkyl acrylates (a1) can use one or more.
As above-mentioned carboxylic monomer (a2), for example can list (methyl) vinylformic acid, Ba Dousuan, toxilic acid, maleic anhydride, methylene-succinic acid, fumaric acid, acrylamide-N-oxyacetic acid, styracin, (methyl) acrylic acid Michael addition thing (acrylic acid dimer for example, the methacrylic acid dimer, the vinylformic acid tripolymer, the methacrylic acid tripolymer, the vinylformic acid tetramer, the methacrylic acid tetramer etc.), 2-(methyl) acryloxy ethyl dicarboxylic acid monoesters (2-acryloxy ethyl monomester succinate for example, 2-methacryloxyethyl monomester succinate, 2-acryloxy ethyl phthalic monoester, 2-methacryloxyethyl phthalic monoester, 2-acryloxy ethyl hexahydrophthalic acid monoesters, 2-methacryloxyethyl hexahydrophthalic acid monoesters etc.) carboxylic unsaturated monomer etc. such as.Preferred (methyl) vinylformic acid that uses.Above-claimed cpd can use one or more.
In addition, as above-mentioned other co-polymerized monomer (a3) that uses as required, for example can list the unsaturated monomer of hydroxyls such as vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, vinylformic acid 3-chloro-2-hydroxypropyl acrylate, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-chloro-2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid binaryglycol ester, (methyl) polyalkylene glycol acrylate ester, N hydroxymethyl acrylamide, N-methylol methacrylamide; (methyl) glycidyl acrylate, (methyl) vinylformic acid allyl glycidyl etc. contain the unsaturated monomer of glycidyl; (methyl) vinylformic acid tertiary butyl amino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid dimethylamino ethyl ester etc. contain amino monomer; (methyl) vinylformic acid 2-(acetoacetoxy groups) ethyl ester, acetoacetic acid allyl ester etc. contain the monomer of acetoacetyl; Alkoxyl group (gathering) alkylene glycol mono (methyl) esters of acrylic acids such as (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 3-methoxyl group ethyl ester, (methyl) vinylformic acid methoxyl group binaryglycol ester; Allylic cpd classes such as N-(methyl) acrylamide methyl trimethoxy ammonium chloride, allyl group trimethyl ammonium chloride, dimethyl-allyl vinyl ketone; Ethene base system monomers such as N-vinyl pyrrolidone, propionate, stearic acid vinyl ester, vinylchlorid, vinylidene chloride, vinyl acetate, vinylbenzene; Vinyl cyanide, n-dodecyl mercaptan etc.Preferred vinyl cyanide, the n-dodecyl mercaptan of using.These compounds can use a kind of or make up two or more uses.
Like this, employed carboxylic acrylic acid polymer (A) can be by with above-mentioned (methyl) alkyl acrylate (a1), carboxylic monomer (a2) and the incompatible acquisition of other co-polymerized monomer (a3) copolymerization as required among the present invention.As its concrete copolymerization component proportions, with respect to all copolymerization compositions, (methyl) acrylic ester monomer (a1) that preferably contains 75～95 weight %, especially 80～93 weight %, particularly 85～90 weight %, the carboxylic monomer (a2) that preferably contains 1～10 weight %, especially 1.5～8 weight %, particularly 2～6 weight % preferably contains other copolymerization monomer (a3) of 5～15 weight %, especially 6～14 weight %, particularly 7～13 weight %.
The weight-average molecular weight (Mw) of the above-mentioned carboxylic acrylic acid polymer (A) of Huo Deing is preferably below 100,000 like this, especially is preferably below 80,000, more preferably below 60,000.This is because when the weight-average molecular weight (Mw) of carboxylic acrylic acid polymer (A) is excessive, can see that resin viscosity raises, the tendency of coating variation.
On the other hand, the lower limit of the weight-average molecular weight (Mw) of carboxylic acrylic acid polymer (A) is preferably more than 10,000, especially is preferably more than 20,000, more preferably more than 30,000.This is because when the weight-average molecular weight (Mw) of carboxylic acrylic acid polymer (A) is too small, can see the force of cohesion deficiency of the tackiness agent that obtains by the active energy beam irradiation, the tendency that binding property reduces.
Above-mentioned carboxylic acrylic acid polymer (A) can well known to a person skilled in the art method manufacturing by solution free radical polymerization, suspension polymerization, mass polymerization, letex polymerization etc.Wherein, suspension polymerization can obtain the big polymkeric substance of the polymerization degree, and in addition, the separation of the polymkeric substance that generates is also easy, therefore, preferably uses as the manufacture method of the carboxylic acrylic acid polymer (A) that satisfies above-mentioned condition.That is, as above-mentioned carboxylic acrylic acid polymer (A), the dried resin that obtains by suspension polymerization (dry resin) preferably.
In addition, when above-mentioned polymerization, as required, can add polymerization starters such as azobis isobutyronitrile.
In addition, in the present invention, the second-order transition temperature (Tg) of carboxylic acrylic acid polymer (A) be preferably-60 ℃～below 20 ℃, especially be preferably-60 ℃～0 ℃, more preferably-55 ℃～below-10 ℃.This be because, cross when low at the second-order transition temperature (Tg) of acrylic acid polymer (A), can see the tendency of force of cohesion variation, on the contrary, when too high, can see the tendency that causes the crisp materialization of tackiness agent.
In addition, in the present invention, weight-average molecular weight is the weight-average molecular weight that converts according to the polystyrene standard molecular weight, by going up the pillar that uses three series connection at high performance liquid chromatograph (Japanese Waters company makes, " Waters 2695 (body) " and " Waters 2414 (detector) "): Shodex GPC KF-806L (eliminating boundary molecular weight: 2 * 10
7, separating ranges: 100～2 * 10
7, number of theoretical plates: 10000 sections/root, weighting agent material: styrene diethylene benzene copoly mer, weighting agent particle diameter: 10 μ m) measure.In addition, second-order transition temperature is calculated by the Fox formula.
With respect to 100 parts above-mentioned active energy ray-curable composition (B), the content of above-mentioned carboxylic acrylic acid polymer (A) is preferably 5～45 parts, especially is preferably 7～35 parts, more preferably 10～25 parts.This is because find, when the content of above-mentioned carboxylic acrylic acid polymer (A) is very few, have and to obtain sufficient fusible tendency, on the contrary, in the time of too much, gained pressure sensitive adhesion of the present invention films to form with composition has the sense of being clamminess to strengthen, and glossiness also reduces, perhaps when peeling off, cross and by force paper takes place and break owing to binding property, perhaps the tendency of the anti-adhesive deficiency of White Board.
" active energy ray-curable composition (B) "
Active energy ray-curable composition (B) is the composition by active energy beam generation curing reaction, preferably is selected from least a active energy ray-curable composition in the following group of forming: at least a (b1) in epoxy (methyl) acrylate and urethane (methyl) acrylate; The alefinically unsaturated compounds except (b1) (b2) (following abbreviate as sometimes " polyfunctional compound (b2)) with 2 above ethylenically unsaturated groups; And the alefinically unsaturated compounds except (b1) (b3) (following abbreviate as sometimes " monofunctional compound (b3) ") with an ethylenically unsaturated group.Especially, and separability good viewpoint when peeling off excellent from bounding force, preferably, contain above-mentioned (b1)～(b3) whole three kinds of compositions, from promoting the viewpoint of curing reaction, further preferably, above-mentioned polyfunctional compound (b2) and monofunctional compound (b3) make up two or more uses respectively.In addition, from obtaining the viewpoint of sufficient resin force of cohesion, more preferably, polyfunctional compound's (b2) content is more than the content of monofunctional compound (b3).
Then, above-mentioned (b1)～(b3) composition is described.
At least a (b1) of＜epoxy (methyl) acrylate and urethane (methyl) acrylate 〉
In the present invention, as the formation compound of active energy ray-curable composition (B), preferably contain at least a (b1) in epoxy (methyl) acrylate and urethane (methyl) acrylate.
This be because, even irradiation low dosage ultraviolet ray amount, above-mentioned epoxy (methyl) acrylate also can solidify at a high speed, in addition, under the situation that cooperates epoxy (methyl) acrylate, as the mechanical properties of product, can see the tendency that the resistance to fatigue of the bending, impact etc. of postcard product becomes excellent.That is, this is because epoxy (methyl) acrylate makes the toughness of rapidly-curable and tackiness agent overlay film become excellent.
Above-mentioned urethane (methyl) acrylate is because its molecular skeleton is pliable and tough, can give the characteristic of product with flexibility, snappiness and so on, in addition, exist greatly as the tensile elongation of mechanical properties, and the resistance to fatigue of the bending of postcard product, impact etc. becomes excellent tendency.
As mentioned above, preferably, use separately epoxy (methyl) acrylate or urethane (methyl) acrylate, perhaps the two is used in combination with epoxy (methyl) acrylate and urethane (methyl) acrylate, the especially preferred epoxy (methyl) of use separately acrylate.
As above-mentioned epoxy (methyl) acrylate, for example can listing, reaction product, multi-functional epoxy compound and (methyl) acrylic acid reaction product, the glycerine polyglycidyl ether of diglycidylether two (methyl) acrylate, multi-functional epoxy compound and (methyl) vinylformic acid and the methyl tetrahydrophthalic anhydride of dihydroxyphenyl propane gather (methyl) acrylate etc.In the middle of these, from the viewpoint of mechanical properties, especially preferred viscosities is 100～1000000mPas/25 ℃, and further preferred viscosities is 1000～100000mPas/25 ℃.
On the other hand, as above-mentioned urethane (methyl) acrylate, for example can list polyoxyalkylene segment or saturated polyester segment or these two connects by urethane bond, have urethane (methyl) acrylate of (methyl) acryl etc. at two ends.In the middle of these, from the viewpoint of mechanical properties, preferred viscosities is 100～100000mPas/60 ℃, and further preferred viscosities is 1000～10000mPas/60 ℃.
In the present invention, viscosity refers to use Brookfield viscometer (ProductName: Brookfield viscometer; Tokyo gauge society makes) (for example 25 ℃, 60 ℃ etc.) are measured under specific temperature condition viscosity.
＜have an alefinically unsaturated compounds except (b1) (b2) of two ethylenically unsaturated groups 〉
The above-mentioned alefinically unsaturated compounds except (b1) (polyfunctional compound (b2)) with two ethylenically unsaturated groups is filmed and is formed copolymerization compound use with the active energy ray-curable composition (B) that uses in the composition as being formed in pressure sensitive adhesion of the present invention, is the polyfunctional compound with two above ethylenically unsaturated groups.
As the polyfunctional compound who uses among the present invention (b2), can list for example multifunctional (methyl) acrylic ester monomer etc.Particularly, can list ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, TEG two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, bisphenol A-type two (methyl) acrylate of oxyethane modification, bisphenol A-type two (methyl) acrylate of epoxy pronane modification, 1,6-hexylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, (methyl) propenyl based compound of two senses such as neopentyl glycol two (methyl) acrylate of hydroxy new pentane acid modification; Trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, three (methyl) acryloyl-oxy base oxethyl TriMethylolPropane(TMP), three (methyl) acrylate of TriMethylolPropane(TMP) oxyethane modification, three (methyl) acrylate of TriMethylolPropane(TMP) epoxy pronane modification, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate of caprolactone modification, (methyl) propenyl based compound that trifunctionals such as Dipentaerythritol six (methyl) acrylate of caprolactone modification are above.Wherein, preferably use 1,6-hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate.They can use one or more, the especially two or more uses of preferably combination.
＜have an alefinically unsaturated compounds except (b1) (b3) of an ethylenically unsaturated group 〉
The above-mentioned alefinically unsaturated compounds except (b1) (b3) (monofunctional compound (b3)) with an ethylenically unsaturated group is filmed and is formed copolymerization compound use with the active energy ray-curable composition (B) that uses in the composition as being formed in pressure sensitive adhesion of the present invention, is the monofunctional compound with an ethylenically unsaturated group.As monofunctional compound (b3), can list (methyl) alkyl acrylate (β-1) and other monofunctional compound (β-2), from effect, preferably use as the monomer mixture that the two is mixed.
As above-mentioned (methyl) alkyl acrylate (β-1), especially can to list the alkyl carbon number be 1～20, be preferably (methyl) alkyl acrylate of 2～18, more preferably 4～10.Particularly, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate etc., from effect, especially preferably use (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, (methyl) n-butyl acrylate.These (methyl) alkyl acrylates (β-1) can use one or more.
As other monofunctional compound (β-2), for example can list (methyl) vinylformic acid, Ba Dousuan, toxilic acid, maleic anhydride, methylene-succinic acid, fumaric acid, (methyl) acrylamide-N-oxyacetic acid, styracin, (methyl) acrylic acid Michael addition thing (acrylic acid dimer for example, the methacrylic acid dimer, the vinylformic acid tripolymer, the methacrylic acid tripolymer, the vinylformic acid tetramer, the methacrylic acid tetramer etc.), 2-(methyl) acryloxy ethyl dicarboxylic acid monoesters (2-acryloxy ethyl monomester succinate for example, 2-methacryloxyethyl monomester succinate, 2-acryloxy ethyl phthalic monoester, 2-methacryloxyethyl phthalic monoester, 2-acryloxy ethyl hexahydrophthalic acid monoesters, 2-methacryloxyethyl hexahydrophthalic acid monoesters etc.) carboxylic unsaturated compound such as; The unsaturated compound of hydroxyls such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-chloro-2-hydroxypropyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid binaryglycol ester, (methyl) polyalkylene glycol acrylate ester, N-methylol (methyl) acrylamide; (methyl) vinylformic acid tertiary butyl amino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid dimethylamino ethyl ester etc. contain amino compound; (methyl) vinylformic acid 2-acetoacetoxy groups ethyl ester, acetoacetic acid allyl ester etc. contain alkoxyl group (gathering) alkylene glycol mono (methyl) esters of acrylic acids such as the compound, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 3-methoxyl group ethyl ester, methoxyl group Diethylene Glycol (methyl) acrylate of acetoacetyl; Allylic cpd classes such as N-(methyl) acrylamide methyl trimethoxy ammonium chloride, allyl group trimethyl ammonium chloride, dimethyl-allyl vinyl ketone; Ethene base system monomers such as N-vinyl pyrrolidone, propionate, stearic acid vinyl ester, vinylchlorid, vinylidene chloride, vinyl acetate, vinylbenzene; (methyl) acrylic acid alkyl ester compound except (β-1) such as phenol ring oxidative ethane modification (methyl) acrylate etc. can be used to be selected from the middle of these one or more.
Especially in requiring the purposes of bounding force, in 100 parts of monofunctional compound (b3), as other monofunctional compound (β-2), it is desirable to contain 1～20 part carboxylic unsaturated compound, be preferably (methyl) vinylformic acid, Ba Dousuan, toxilic acid, maleic anhydride, methylene-succinic acid, fumaric acid, (methyl) acrylamide-N-oxyacetic acid, styracin, be preferably (methyl) vinylformic acid especially.
Like this, as active energy ray-curable composition (B), be preferably and be selected from least a in the group of being formed by at least a (b1), polyfunctional compound (b2) and monofunctional compound (b3) in above-mentioned epoxy (methyl) acrylate and urethane (methyl) acrylate, especially preferably contain above-mentioned (b1)～(b3) whole three kinds of compositions.
When stating (b1)～(b3) three kinds of compositions in the use, all with respect to above-mentioned active energy ray-curable composition (B), containing of various compositions proportionally preferably is set as follows respectively: (b1) composition is preferably 5～20 weight %, especially is preferably 6～18 weight %, 7～16 weight % more preferably, (b2) composition is preferably 40～80 weight %, especially is preferably 45～75 weight %, 50～70 weight % more preferably, and (b3) composition is preferably 10～40 weight %, especially is preferably 13～35 weight %, 15～30 weight % more preferably.
At least a (b1) in above-mentioned epoxy (methyl) acrylate and urethane (methyl) acrylate gives and filming with mechanical properties, is the composition that surface hardness, flexibility are exerted an influence.Therefore, (b1) composition contain proportionally when very few, found following tendency: the sense of being clamminess of filming strengthens, binding property is crossed strong and paper takes place is broken when peeling off, perhaps the resistance to blocking of White Board is also not enough.On the contrary, in the time of too much, film coated surface hardness is too high, therefore, and the tendency of having filmed and having split when having found bending.Found that in addition binding property also reduces, can not obtain the tendency of suitable bond strength.
In addition, above-mentioned polyfunctional compound (b2) improves the composition that reinforcement etc. has the linking agent effect.Therefore, (b2) composition contain proportional visible following tendency when very few, that is, and the force of cohesion deficiency of resin, the sense of being clamminess strengthens, and glossiness also reduces, binding property is crossed strong and the tendency that paper breaks is taken place when perhaps peeling off; On the contrary, in the time of too much, can see the tendency that the force of cohesion of resin increases, binding property weakens.
In addition, above-mentioned monofunctional compound (b3) is the dispersion agent of acrylic rubber, and is to shine and the force of cohesion of polymerization, control resin and the composition of second-order transition temperature (Tg) by ultraviolet isoreactivity energy-ray.Therefore, found following tendency, that is, (b3) composition contain proportional when very few, aforementioned (b1) composition or have the linking agent effect (b2) composition contain proportional relative increase, therefore, the force of cohesion of resin becomes too high, binding property weakens; On the contrary, in the time of too much, the force of cohesion deficiency of resin, the tendency of the smoothness of film coated surface forfeiture when peeling off.
" Photoepolymerizationinitiater initiater (C) "
The Photoepolymerizationinitiater initiater that uses among the present invention (C) can use the Photoepolymerizationinitiater initiater of intramolecularly autothermic cracking type Photoepolymerizationinitiater initiater or hydrogen-abstraction so long as the effect by light isoreactivity energy-ray produces the initiator of free radical just is not particularly limited.
Photoepolymerizationinitiater initiater as above-mentioned intramolecularly autothermic cracking type; can list for example 4-phenoxy group Er Lvyixianben; the 4-tertiary butyl-Er Lvyixianben; the diethoxy phenyl methyl ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1 ketone; 1-(4-isopropylidene phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone; 1-hydroxyl-cyclohexyl-phenyl-ketone; 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl propane-1-ketone; bitter almond oil camphor; benzoin methylether; ethoxybenzoin; the bitter almond oil camphor isopropyl ether; the bitter almond oil camphor isobutyl ether; benzoin dimethylether; α-acyl group oxime ester (acyloxime ester); acylphosphine oxide; methyl benzoylformate (methyl phenyl glyoxylate); 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone; 4-benzoyl-4 '-methyldiphenyl thioether etc.; wherein, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-hydroxyl-cyclohexyl-phenyl-ketone is preferred.
In addition; Photoepolymerizationinitiater initiater as above-mentioned hydrogen-abstraction; for example can list benzophenone; the benzoyl phenylformic acid; the benzoyl methyl benzoate; the 4-phenyl benzophenone; dihydroxy benaophenonel; 3; 3 '-dimethyl-4-methoxy benzophenone; 2; 4; the 6-tri-methyl benzophenone; 4-methyldiphenyl ketone; thioxanthone; the 2-clopenthixal ketone; 2-methyl thioxanthone; 2; 4-dimethyl thioxanthone; isopropyl thioxanthone; camphorquinone; dibenzosuberone (dibenzosuberone); 2-ethyl-anthraquinone; 3; 3 '; 4; 4 '-four (tert-butyl peroxide carbonyl) benzophenone; benzoin dimethylether; 9; 10-phenanthrenequione etc.; preferred benzophenone wherein; the methyldiphenyl ketone; 2,4,6-tri-methyl benzophenone.
These Photoepolymerizationinitiater initiaters (C) can use a kind of or make up two or more uses.
Further, as required, auxiliary agent as Photoepolymerizationinitiater initiater (C), can be used in combination trolamine, tri-isopropanolamine, 4 effectively, 4 '-dimethylamino benzophenone (Michler's keton), 4,4 '-diethylamino benzophenone, phenylformic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone etc.
With respect to 100 parts of above-mentioned active energy ray-curable compositions (B), the content of above-mentioned Photoepolymerizationinitiater initiater (C) is 10～30 parts, is preferably 13～27 parts, is preferably 16～25 parts especially.When the content of Photoepolymerizationinitiater initiater was lower than above-mentioned lower value, the polymerization imbalance appearred easily; On the contrary, when surpassing above-mentioned higher limit, will not produce binding property, thereby become impracticable.
" additive "
In addition, in the present invention, in the scope of not damaging effect of the present invention, can add other tackiness agent, urethane resin, rosin, rosin ester, hydrogenated wood rosin glycerol ester, resol, the aromatic series modified terpene resin, aliphatics through-stone oleo-resinous, alicyclic through-stone oleo-resinous, phenylethylene resin series, tackifier such as diformazan benzene series resin, and stopper, viscosity modifier, flow agent, wax, defoamer, antiaging agent, stablizer, tinting material, known additives such as particulate weighting agent cause colour developing or the compound of variable color by ultraviolet ray or radiation exposure.
By using the mentioned component material, can obtain active energy ray curable pressure sensitive adhesion of the present invention and film to form and use composition.
" the active energy ray curable pressure sensitive adhesion is filmed to form and is used composition "
Active energy ray curable pressure sensitive adhesion of the present invention is filmed to form and is not contained water, aqueous solvent or organic solvent in fact with composition, and other composition of carboxylic acrylic acid polymer (A) and Photoepolymerizationinitiater initiater (C) and interpolation as required dissolves in active energy ray-curable composition (B) or becomes homodisperse state.This active energy ray curable pressure sensitive adhesion film form with composition can by with carboxylic acrylic acid polymer (A), active energy ray-curable composition (B), Photoepolymerizationinitiater initiater (C) and other composition of adding as required under normal temperature (about 25 ℃ ± 10), according to circumstances be heated in the temperature range of normal temperature～60 ℃ and mix and prepare.
The gained active energy ray curable pressure sensitive adhesion viscosity that forms with composition of filming is preferably 100～500mPas/25 ℃.This be because, when viscosity is too high, finds to have and be difficult to the evenly tendency of coating, on the contrary, cross when low in viscosity, find the suitable property variation of coating, and be difficult to obtain the tendency of uniform coating.
The gained active energy ray curable pressure sensitive adhesion apparatus for coating such as forming the machine that is coated with by intaglio plate coating machine, flexographic plate coating machine, Kohler coater, rod with composition of filming is coated on printing sheets, the whole binding face or established part of postcard with substrate papers such as paper, then, to its irradiation active energy beam, form the bonding coat that appropriateness is solidified.And, the bonding coat of above-mentioned curing is overlapped, for example by pressure sensitive adhesion under the pressure of regulation such as backer roll, can form and have the bonding of separability.
Wherein, form the substrate paper of the coating object of using composition as constituting of the present invention filming, can list for example vellum, medium paper, rough paper, cotton paper, enamelled paper (art paper), White Board (coated paper), light weight coated paper, plastic layer platen, cloth, plastic layer compress, plastics film, tinsel etc.
As mentioned above, after active energy beam irradiation, carry out under the situation of overlapping, pressure sensitive adhesion, hinder this principal element in order to get rid of the polymerization that when active energy beam shines, is caused by oxygen, more preferably under atmosphere of inert gases, shine active energy beam, consider that the polymerization that is caused by oxygen hinders this principal element, can also adjust illuminate condition to obtain physical properties balance.
" active energy beam "
In above-mentioned, as active energy beam, can utilize hertzian wave such as light such as far ultraviolet rays yue, ultraviolet ray, near-ultraviolet ray, infrared rays, X ray, gamma-rays and electron rays, proton ray, neutron ray etc., from considerations such as the easiness of the acquisition of curing speed, irradiating unit, prices, be favourable with the curing of uviolizing.
In uviolizing, can use high voltage mercury lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp of the light that sends 150～450nm wavelength region etc.
In the present invention, the irradiation dose as active energy beam is preferably 500mJ/cm
2More than be preferred, especially be preferably 1000mJ/cm
2More than, 1500mJ/cm more preferably
2More than.This irradiation dose is crossed when hanging down, and has found to be easy to generate unbalanced tendency in the polymerization of using the active energy beam irradiation.In addition, the upper limit of irradiation dose is generally 10000mJ/cm
2This is because when irradiation dose is too much, found unpractical tendency in the relation of device and cost.
In addition, require difference by the thickness that is coated with the bonding coat that obtains according to purposes, therefore can not limit entirely, but be preferably 5～200 μ m, more preferably 10～150 μ m.This is because the thickness of bonding coat is crossed when thin, finds that bonding rerum natura is difficult to stable tendency, on the contrary, when blocked up, has found to be easy to generate the tendency of adhesive residue.
Embodiment
Below be described more specifically the present invention with embodiment, yet only otherwise exceed its purport, the present invention is not limited by the following examples.
Wherein, " part ", " % " in the example refer to weight basis, unless otherwise prescribed.
The preparation of＜acrylic acid polymer 〉
[Production Example 1:A composition (embodiment uses)]
In the poly-unit that is provided with stirrer, thermometer, condenser, add 250 parts of deionized waters and stir, add and dissolve 0.6 part the polyvinyl alcohol as dispersion stabilizer.After this, when stirring, to the azobis isobutyronitrile as polymerization starter that wherein adds 2.5 parts of vinylformic acid, 10 parts of vinyl cyanide, 77.5 parts of n-butyl acrylates, 10 parts of methyl methacrylates, 0.5 part of n-dodecyl mercaptan and 0.4 part.Then, content is warming up to 75 ℃, keeps 75 ℃ of temperature of reaction, reacted 3 hours.After this, be warming up to 90 ℃, kept this temperature 1 hour, finish reaction.Then, with this reactant of filter cloth filtration washing of 10 μ m perforates, with 50 ℃ circulating air drying machine drying, obtain carboxylic acrylic acid polymer (A composition).
The weight-average molecular weight of the carboxylic acrylic acid polymer of gained (Mw) is 80,000, and second-order transition temperature is-50 ℃.
(Production Example 2: comparative example is used)
At four neck round-bottomed flasks reflux cooler, agitator, dropping funnel and thermometer are installed, add 88 parts of n-butyl acrylates, 7 parts of vinyl cyanide, 5 parts of methacrylic acid 2-hydroxyl ethyl esters and 80 parts of vinyl acetic monomers, after reflux begins, add 0.06 part of azobis isobutyronitrile as polymerization starter, reaction is 2 hours under the vinyl acetic monomer reflux temperature, be added on the solution that is dissolved with 0.07 part of azobis isobutyronitrile in 5 parts of toluene then, further under reflux temperature, reacted 5 hours.After this, use drying machine that this reactant was descended dry 12 hours at 70 ℃, obtain the acrylic acid polymer that not carboxylic comparative example is used.
The weight-average molecular weight of the acrylic acid polymer of gained (Mw) is 400,000, and second-order transition temperature is-40 ℃.
Use each acrylic acid polymer that obtains by above-mentioned Production Example, according to following embodiment and comparative example, make each active energy ray curable pressure sensitive adhesion formation composition of filming.
[embodiment 1]
In having the container of stirrer, drop into the carboxylic acrylic acid polymer that obtains in 13 parts the Production Example 1, as 13 parts of epoxy acrylates (trade(brand)name: " CN-116 " of (b1) composition; Sartomer company makes), as 22 parts of Viscoat 295s of polyfunctional compound (b2), 40 part 1, the 6-hexanediyl ester is as 11 parts of n-butyl acrylates of monofunctional compound (b3), 14 parts of vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester (trade(brand)names: " ARONIX M-5700 "; The synthetic society in East Asia makes), mixed dissolving 24 hours.The viscosity of this solution is 150mPas/25 ℃.
In this solution, mix the 16 parts of 1-hydroxyl-cyclohexyl-phenyl-ketone (trade(brand)name " Irgacure 184 " as Photoepolymerizationinitiater initiater (C); The manufacturing of Ciba Specialty Chemicals company), 1 part of 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl propane-1-ketone (trade(brand)name: " Irgacure 907 "; Ciba Specialty Chemicals company makes), the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and is used composition.
[embodiment 2]
Except using the carboxylic acrylic acid polymer that obtains in 14 parts the Production Example 1, as 26 parts of Viscoat 295s of polyfunctional compound (b2), 43 part 1, the 6-hexanediyl ester is as 14 parts of n-butyl acrylates of monofunctional compound (b3), 17 parts of vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester (trade(brand)names: " ARONIXM-5700 "; The synthetic society in East Asia makes) in addition, similarly to Example 1, the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and is used composition.
[embodiment 3]
Except using the carboxylic acrylic acid polymer that obtains in 14 parts the Production Example 1, as 14 parts of epoxy acrylates (trade(brand)name: " CN-116 " of (b1) composition; Sartomer company makes), 63 parts of 1,6 hexanediol diacrylates, as 10 parts of n-butyl acrylates of monofunctional compound (b3), 13 parts of vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester (trade(brand)names: " ARONIX M-5700 "; The synthetic society in East Asia makes) in addition, similarly to Example 1, the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and is used composition.
[comparative example 1]
Except Photoepolymerizationinitiater initiater being set at 6 parts of 1-hydroxyl-cyclohexyl-phenyl-ketone (trade(brand)name " Irgacure 184 "; Ciba Specialty Chemicals company makes) in addition, similarly to Example 1, the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and is used composition.
[comparative example 2]
Except Photoepolymerizationinitiater initiater being set at 6 parts of 2-hydroxy-2-methyl-phenyl-propane-1-ketone (trade(brand)name " D-1173 "; Ciba Specialty Chemicals company makes) in addition, similarly to Example 1, the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and is used composition.
[comparative example 3]
Except Photoepolymerizationinitiater initiater being set at 6 parts of 2-methyl isophthalic acids-(4-methylthio group phenyl)-2-morpholinyl propane-1-ketone (trade(brand)name: " Irgacure 907 "; Ciba SpecialtyChemicals company makes) in addition, similarly to Example 1, the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and is used composition.
[comparative example 4]
The comparative example that obtains in using Production Example 2 is with the acrylic acid polymer, and similarly to Example 1, the pressure sensitive adhesion of acquisition active energy ray curable is filmed to form and used composition.In addition, the viscosity of the solution before the interpolation Photoepolymerizationinitiater initiater is 1300mPas/25 ℃.
Following table 1 shows the cooperation ratio of above-mentioned each the composition material that uses in embodiment and the comparative example.
[table 1]
(weight part)
The active energy ray curable pressure sensitive adhesion that obtains in use the various embodiments described above and the comparative example is filmed to form and is used composition, makes the bonding converted paper of separability by following method.
Excellent with 7g/m by winding the line
2Ratio the active energy ray curable pressure sensitive adhesion that obtains in each embodiment and the comparative example filmed to form coat basic weight 110g/m with composition
2White Board on, form bonding coat by the curing of using uviolizing, obtain the bonding converted paper of each separability.The uviolizing condition is: use high voltage mercury lamp, the about 200W/m of exposure intensity
2, accumulation illumination 60mJ/m
2, lamp height 18cm.
Use the bonding converted paper of each separability of above-mentioned acquisition, estimate coating and solidified nature.
(coating)
Observe the coated face of the bonding converted paper of separability, judge its coating state according to following benchmark.
Zero: whole surface evenly is coated with, and is glossy.
△: seen a small amount of disorder at coated face, but do not had the problem in the practicality.
*: because Combination difference or the viscosity height of composition, the visible fragmentary disorder of coated face, slit etc.
(solidified nature)
Confirm being clamminess of coated face, hardness of the bonding converted paper of separability etc., judge the solid state of its bonding coat according to following benchmark.
Zero: do not have and be clamminess, finish curing fully.
△: solidify basically, but some parts that are clamminess are arranged.
*: the part that is clamminess is many, and scraping is just peeled off gently, for solidifying bad state.
Then, be width 25mm, length 100mm with the bonding converted paper severing of above-mentioned separability, with its 2 overlapping, coated face is mutually combined, use laminating machine with the pressure pressure sensitive adhesion of 0.2MPa, make the test portion (interim pasted paper pressurizes) of width 25mm.
Use the interim pasted paper that respectively pressurizes of above-mentioned acquisition, estimate binding property.
(binding property)
The interim pasted paper bending of will pressurizeing, that confirms to have or not adhesive face peels off, floats etc. bonding bad, judges its tacky state according to following benchmark.
◎: bonding fully, even bending, bond site is not peeled off yet.
Zero: bonding basically, can fully be used for purposes of the present invention.
△: though roughly bonding, a little less than, according to the quality of paper, if the bending, adhesive face floats disengaging sometimes.
*: bonding weak or do not have bonding fully.
And then, use the interim pasted paper of above-mentioned pressurization, estimate separability according to following method.
Under peeling rate 300mm/min, 23 ℃, the condition determination of relative humidity 50%, use omnipotent determinator (trade(brand)name: " Autograph "; Society of Shimadzu Seisakusho Ltd. makes) the interim pasted paper of the pressurization of width 25mm is carried out the stripping test of T type.
(separability)
The state of peeling off when judging above-mentioned T type stripping test according to following benchmark.
Zero: peel off and do not have paper to break.
△: do not have paper to break though peel off, stripping strength is big, according to papery, rupture line is arranged sometimes on the coated surface on surface.
*: bonding, attempt to peel off, then paper breaks.
-: owing to from the most bonding from the beginning of not having, therefore can not judge.
The evaluation result of the coating of above-mentioned acquisition, solidified nature, binding property, separability is shown in the following table 2.
[table 2]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Coating | ○ | ○ | ○ | ○ | ○ | ○ | × |
| Solidified nature | ○ | ○ | △ | × | × | × | ○ |
| Binding property | ◎ | △ | ○ | × | × | × | ○ |
| Separability | ○ | △ | △ | - | - | - | × |
From The above results as can be seen, the bonding converted paper of separability that obtains among the embodiment 1 has excellent coating, solidified nature, binding property, separability, practicality height.Though embodiment 2 does not cooperate any as epoxy (methyl) acrylate of (b1) composition and urethane (methyl) acrylate, in addition, embodiment 3 has only cooperated a kind of polyfunctional compound (b2), but coating, the solidified nature of embodiment 2 are good, coating, the binding property of embodiment 3 are good, and other rerum natura such as separability also can be practical.In addition, in these embodiments, the drying process when not needing to be coated with, visible excellent surface luster on the printing surface.
In contrast, the comparative example 1～3 of ordinary light polymerization starter content is because curing is bad, and binding property is far from being fully.In addition, in using the comparative example 4 of carboxylic acrylic acid polymer not, the pressure sensitive adhesion Combination that forms with composition of filming is poor, and coating is inferior, and binding property is too high, therefore attempts to peel off, and then paper breaks.
Utilizability on the industry
Active energy ray curable pressure sensitive adhesion of the present invention is filmed to form and be can be used as the tackiness agent that uses with composition in having the postcard system of personal delivery, this postcard system replaces sealing letter and is used for realizing postal cost reduces, information is printed and the notice thing is made automatization etc., in addition, by being coated with in substrate sheets such as non-woven fabrics, foam substrates etc., can also use as double sticky tape, self adhesive tape.
Claims (5)
1. an active energy ray curable pressure sensitive adhesion is filmed to form and is used composition, it is characterized in that, described composition contains carboxylic acrylic acid polymer (A), active energy ray-curable composition (B) and Photoepolymerizationinitiater initiater (C), described active energy ray-curable composition (B) with respect to 100 weight parts, the content of described Photoepolymerizationinitiater initiater (C) is 10～30 weight parts
Described active energy ray-curable composition (B) contains following b1～b3, and is all with respect to described active energy ray-curable composition (B), and containing of b1～b3 proportionally is: b1 is that 5～20 weight %, b2 are that 40～80 weight % and b3 are 10～40 weight %,
B1: at least a in epoxy (methyl) acrylate and urethane (methyl) acrylate;
B2: the alefinically unsaturated compounds except b1 with 2 above ethylenically unsaturated groups;
B3: the alefinically unsaturated compounds except b1 with an ethylenically unsaturated group.
2. active energy ray curable pressure sensitive adhesion according to claim 1 is filmed to form and is used composition, it is characterized in that the weight-average molecular weight of carboxylic acrylic acid polymer (A) is below 100,000.
3. active energy ray curable pressure sensitive adhesion according to claim 1 is filmed to form and is used composition, it is characterized in that the second-order transition temperature of carboxylic acrylic acid polymer (A) is-60 ℃～20 ℃ scope.
4. active energy ray curable pressure sensitive adhesion according to claim 1 is filmed to form and is used composition, it is characterized in that, with respect to the described active energy ray-curable composition (B) of 100 weight parts, carboxylic acrylic acid polymer (A) to contain proportional be 5～45 weight parts.
5. the bonding converted paper of separability is characterized in that, it is each described active energy ray curable pressure sensitive adhesion of claim 1～4 to be filmed to form coat on the paper surface with composition, and obtains with active energy beam curing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-340017 | 2007-12-28 | ||
| JP2007340017A JP5528669B2 (en) | 2007-12-28 | 2007-12-28 | A composition for forming an active energy ray-curable pressure-sensitive adhesive coating film and a peelable adhesive-processed paper using the same. |
| PCT/JP2008/073332 WO2009084511A1 (en) | 2007-12-28 | 2008-12-22 | Composition for forming contact-bonding coating film of actinic-energy-ray curable type and strippable adhesive-coated paper employing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101855310A CN101855310A (en) | 2010-10-06 |
| CN101855310B true CN101855310B (en) | 2013-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200880115150XA Active CN101855310B (en) | 2007-12-28 | 2008-12-22 | Composition for forming contact-bonding coating film of actinic-energy-ray curable type and strippable adhesive-coated paper employing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5528669B2 (en) |
| KR (1) | KR101530400B1 (en) |
| CN (1) | CN101855310B (en) |
| WO (1) | WO2009084511A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5344038B2 (en) * | 2009-07-08 | 2013-11-20 | 東亞合成株式会社 | Thick coating composition |
| JP6051662B2 (en) * | 2012-08-03 | 2016-12-27 | 日立化成株式会社 | Adhesive composition for circuit connection, adhesive sheet, adhesive reel and circuit member connection structure |
| JP6062806B2 (en) * | 2013-05-31 | 2017-01-18 | 昭和電工株式会社 | Active ray curable adhesive composition for re-peeling protective tape for glass etching, re-peeling protective tape for glass etching |
| JP6841044B2 (en) * | 2016-04-20 | 2021-03-10 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-polymerizable adhesive and laminate |
| KR102470448B1 (en) | 2017-12-15 | 2022-11-24 | 주식회사 엘지화학 | Aqueous acrylic adhesive for clothes and method for preparing the same |
| KR20200098401A (en) * | 2019-02-12 | 2020-08-20 | 닛토덴코 가부시키가이샤 | Reinforcing film, method for making device and reinforcing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06346026A (en) * | 1993-06-10 | 1994-12-20 | Mitsui Toatsu Chem Inc | Composition for activating energy ray curing type hot-melt pressure sensitive adhesive and adhesive product using this composition and production of adhesive product |
| JPH108267A (en) * | 1996-06-27 | 1998-01-13 | Nitto Denko Corp | Method for removing resist film image and adhesive material for removing resist |
| JP4030630B2 (en) * | 1997-11-05 | 2008-01-09 | リンテック株式会社 | Adhesive sheet and adhesive sheet bonding method |
| JP4675441B2 (en) * | 1999-01-25 | 2011-04-20 | リンテック株式会社 | Adhesive sheet |
| JP4544658B2 (en) * | 1999-02-02 | 2010-09-15 | 日東電工株式会社 | Semiconductor wafer protective adhesive sheet and semiconductor wafer grinding method |
-
2007
- 2007-12-28 JP JP2007340017A patent/JP5528669B2/en active Active
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2008
- 2008-12-22 KR KR1020107007582A patent/KR101530400B1/en active IP Right Grant
- 2008-12-22 WO PCT/JP2008/073332 patent/WO2009084511A1/en active Application Filing
- 2008-12-22 CN CN200880115150XA patent/CN101855310B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| JP特开2000-212526A 2000.08.02 |
| JP特开平10-8267A 1998.01.13 |
| JP特开平6-346026A 1994.12.20 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101855310A (en) | 2010-10-06 |
| KR20100102091A (en) | 2010-09-20 |
| JP2009161603A (en) | 2009-07-23 |
| JP5528669B2 (en) | 2014-06-25 |
| KR101530400B1 (en) | 2015-06-19 |
| WO2009084511A1 (en) | 2009-07-09 |
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