WO2018037912A1 - 光硬化性樹脂組成物、インキ及び塗料 - Google Patents
光硬化性樹脂組成物、インキ及び塗料 Download PDFInfo
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- WO2018037912A1 WO2018037912A1 PCT/JP2017/028766 JP2017028766W WO2018037912A1 WO 2018037912 A1 WO2018037912 A1 WO 2018037912A1 JP 2017028766 W JP2017028766 W JP 2017028766W WO 2018037912 A1 WO2018037912 A1 WO 2018037912A1
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- resin composition
- photocurable resin
- polymer
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Classifications
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
Definitions
- the present invention relates to a photocurable resin composition containing a polymer (A) obtained by polymerizing a compound represented by the general formula [I], and an ink and a paint comprising the resin composition. More specifically, the present invention relates to a photocurable resin composition having excellent adhesion to a plastic substrate.
- UV-curing type printing inks are highly evaluated and have been put to practical use because of their fast curing speed, which can be cured in a short time, compatibility with the environment because they do not use solvents, and resource and energy savings. It has spread.
- a resin composition containing a diallyl phthalate resin derived from diallyl phthalate (diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate) has been adopted as a UV offset ink for paper. .
- Patent Document 1 An ultraviolet curable inkjet ink composition for a non-absorbing material containing a pigment, an ultraviolet curable resin, and a photopolymerization initiator, wherein the ultraviolet curable resin has a triazine or higher functional allyl group and a polyester acrylate. And (meth) acrylate are described (Patent Document 2).
- Patent Document 2 it is a composition for inkjet, and is insufficient in terms of adhesion to a plastic substrate and drying properties.
- An object of the present invention is to provide a photocurable resin composition containing a polymer (A) having excellent adhesion to a plastic substrate.
- a photocurable resin composition containing a polymer (A) obtained by polymerizing a compound having a specific structure is excellent in adhesion to a plastic substrate.
- the present invention has been conceived.
- the photocurable resin composition of the present invention is It contains a polymer (A) obtained by polymerizing a compound represented by the following general formula [I].
- R 1 represents a [—CH 2 —CR 3 ⁇ CHR 2 ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom
- the photocurable resin composition of the present invention preferably further contains an ethylenically unsaturated compound (B).
- an ethylenically unsaturated compound By using an ethylenically unsaturated compound, the drying property of the photocurable resin composition is improved, the viscosity can be adjusted to be appropriate for use in printing, and the composition has excellent coating workability.
- the photocurable resin composition of the present invention preferably further contains a photopolymerization initiator.
- a photopolymerization initiator By containing a photopolymerization initiator, polymerization by light irradiation proceeds smoothly, so that a cured product can be obtained in a short time.
- the ink of the present invention includes the photocurable resin composition of the present invention.
- This ink is suitable as an ink for printing on a plastic substrate, and particularly suitable as an ink for printing on a substrate such as a PP resin sheet or film.
- the paint of the present invention includes the photocurable resin composition of the present invention.
- This paint is suitable as a paint for drawing on a plastic substrate, and particularly suitable as a paint for drawing on a substrate such as a PP resin sheet or film.
- the coating material of this invention is an overprint varnish.
- a photocurable resin composition having excellent adhesion to a synthetic polymer substrate, particularly a plastic substrate, can be obtained.
- the photocurable resin composition of the present invention comprises a polymer (A) obtained by polymerizing a compound represented by the following general formula [I].
- a polymer (A) obtained by polymerizing a compound represented by the following general formula [I] the reason why the polymer (A) is excellent in adhesion to a synthetic polymer substrate, particularly a plastic substrate, is not clear, but is presumed as follows.
- the structure based on the isocyanurate ring (the ring structure in the following general formula [I] (trimer of isocyanate))
- the structure based on the isocyanurate ring that exists continuously is presumed to be excellent in adhesion to a synthetic polymer substrate, particularly a plastic substrate.
- At least one R 1 is preferably a [—CH 2 —CR 3 ⁇ CHR 2 ] group, and two are preferably [—CH 2 —CR 3 ⁇ CHR 2 ] groups. Is more preferably a [—CH 2 —CR 3 ⁇ CHR 2 ] group. The greater the number of [—CH 2 —CR 3 ⁇ CHR 2 ] groups, the better the reactivity and the easier to obtain a higher molecular weight polymer.
- R 2 and R 3 are preferably H (hydrogen atom), and more preferably H (hydrogen atom).
- R 1 when R 1 is an alkyl group, examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.
- a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, and a methyl group and an ethyl group are more preferable.
- Specific examples of the compound having the structure represented by the general formula [I] include triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoethyl isocyanurate, diallyl monopropyl isocyanurate, trimethallyl isocyanate.
- diallyl isocyanurate monoallyl dimethyl isocyanurate, monoallyl diethyl isocyanurate, monoallyl dipropyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoethyl monomethyl isocyanurate, monoallyl isocyanurate, monoallyl dimethallyl isocyanate Examples thereof include nurate, monoallyl monomethallyl monomethyl isocyanurate, and the like.
- triallyl isocyanurate diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate and diallyl isocyanurate are preferred, triallyl isocyanurate, diallyl monomethyl isocyanurate and diallyl isocyanurate are more preferred, and triallyl isocyanurate is particularly preferred preferable.
- the polymer (A) obtained by polymerizing the compound represented by the above formula [I] can be used for the photocurable resin composition. Furthermore, it is also possible to use what copolymerized the compound represented with the said general formula [I], and another polymerizable compound for a photocurable resin composition.
- acrylic acid esters such as methyl acrylate and butyl acrylate
- various aliphatic and aromatic carboxylic acid vinyl esters such as vinyl acetate, vinyl laurate, vinyl benzoate
- vinyl chloride bromide Vinyls such as vinyl, vinylidenes such as vinylidene chloride and vinylidene bromide
- vinyl alkyl ethers such as methyl vinyl ether and butyl vinyl ether
- allyl ethers such as trimethylolpropane diallyl ether and pentaerythritol triallyl ether
- allyl acetate benzoic acid
- benzoic acid examples thereof include various aliphatic and aromatic carboxylic acid allyl esters such as allyl acid, polybasic acid allyl esters such as diallyl terephthalate and triallyl citrate.
- the blending ratio of the copolymer component in the polymer (A) may be 2 to 50% by weight, and preferably 2 to 20% by weight.
- Examples of methods for obtaining the compounds listed as specific examples of the compounds represented by the above general formula [I] may be synthesized by a generally known polymerization method, or commercially available products may be used.
- the polymerization method of the compound represented by the general formula [I] is not particularly limited, and a normal polymerization reaction can be used.
- a polymerization initiator may be appropriately added to the polymerization reaction as necessary. By using a polymerization initiator, a higher molecular weight polymer (A) can be obtained in a short time.
- Examples of the polymerization initiator used for the polymerization reaction of the compound represented by the general formula [I] include azo initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate, ketone peroxide, peroxyketal, Peroxide initiators such as hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, benzoyl peroxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Acetophenones such as propan-1-one and 1-hydroxycyclohexyl phenyl ketone, benzoins such as benzoin and benzoin ethyl ether, benzophenones such as benzophenone, phosphoruss such as acylphosphine oxide, sulfurs such as thioxanthone, benzyl, 9, 1 Examples thereof include benzyl photopolymerization initiators such as 0-phen
- the amount of the polymerization initiator is preferably 5.0 parts by weight or less and preferably 3.0 parts by weight or less with respect to 100 parts by weight of the monomer of the compound represented by the general formula [I]. More preferred. Further, it is particularly preferably 0.001 to 3.0 parts by weight.
- the reaction temperature during polymerization is preferably 60 to 240 ° C., for example 80 to 220 ° C.
- the reaction time is preferably 0.1 to 100 hours, for example 1 to 30 hours.
- Polymer (A) having a monomer unit based on the compound represented by the general formula [I] can be prepared by polymerizing the compound represented by the general formula [I] by the above-described method or the like.
- the content of the monomer unit based on the compound represented by the general formula [I] is preferably 20% by weight or more, and 50% by weight or more in 100% by weight of the polymer (A). More preferably, it is more preferably 80% by weight or more, particularly preferably 98% by weight or more, and may be 100% by weight.
- the weight average molecular weight (Mw) of the polymer (A) is preferably 250,000 or less, and more preferably 200,000 or less. Moreover, it is preferable that the weight average molecular weights of a polymer (A) are 2,000 or more, and it is more preferable that it is 5,000 or more. The weight average molecular weight of the polymer (A) is more preferably 10,000 to 150,000, and particularly preferably 20,000 to 140,000.
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A) is preferably 1.5 to 10.0, and more preferably 3.0 to 7.5.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer (A) are values measured by the methods described in the examples.
- the content of the polymer (A) in the photocurable resin composition of the present invention is preferably 1 to 50% by weight, and preferably 1 to 40% by weight, based on the total amount of the photocurable resin composition. More preferred is 1 to 30% by weight.
- the lower limit is particularly preferably 1% by weight, and may be 5% by weight.
- content of a polymer (A) exceeds 50 weight%, the solubility to an ethylenically unsaturated compound (B) will worsen, a viscosity may become high and handleability may worsen. If the content of the polymer (A) is less than 1% by weight, sufficient drying properties and adhesion may not be obtained in the resulting photocurable resin composition.
- the photocurable resin composition of the present invention preferably contains an ethylenically unsaturated compound (B) that can be cured by light irradiation.
- the ethylenically unsaturated compound (B) preferably has 1 to 20 carbon-carbon double bonds, more preferably 1 to 10 and even more preferably 2 to 6.
- Examples of the ethylenically unsaturated compound (B) include (meth) acrylic acid ester compounds, (meth) allyl compounds and vinyl compounds.
- the ethylenically unsaturated compound may be a mixture of two or more compounds.
- (meth) acrylic acid ester compounds include pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, 1,6-hexanediol, glycerin, polyethylene glycol, and polypropylene glycol (meta).
- Examples of the (meth) allyl compound include di (meth) allyl phthalate.
- Examples of the vinyl compound include styrene, divinylbenzene, N-vinylpyrrolidone, vinyl acetate and the like.
- ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, and alkylene oxides such as ethylene oxide and propylene oxide were added to them in terms of compatibility with the polymer (A) and curability when photocured. Those are preferred.
- the content of the ethylenically unsaturated compound (B) contained in the photocurable resin composition of the present invention is 50 to 1200 weights with respect to 100 parts by weight of the polymer (A) in the photocurable resin composition. Parts, preferably 50 to 1000 parts by weight, and more preferably 100 to 900 parts by weight.
- the ratio of the polymer (A) to the ethylenically unsaturated compound (B) in the photocurable resin composition of the present invention (polymer: ethylenically unsaturated compound) is 5:95 to 95 by weight. : 5, preferably 10:90 to 90:10, more preferably 10:90 to 70:30, and more preferably 10:90 to 50:50. More preferably it is. If it is in the said range, sufficient adhesiveness to a plastic base material will be easy to be obtained.
- the photocurable resin composition of the present invention may contain a polymerization initiator, and particularly preferably contains a photopolymerization initiator.
- a photopolymerization initiator contained in the photocurable resin composition include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.
- Acetophenone such as benzoin and benzoin ethyl ether
- benzophenone such as benzophenone
- phosphorus such as acylphosphine oxide
- sulfur such as thioxanthone
- benzyl such as benzyl and 9,10-phenanthrenequinone Is mentioned.
- the amount of the photopolymerization initiator contained in the photocurable resin composition is preferably in the range of 0.1 to 15% by weight, and preferably 0.5 to 12% by weight with respect to the entire photocurable resin composition. % Is more preferable, and the range of 1 to 10% by weight is more preferable.
- a photoinitiator for example, an amine photoinitiator such as triethanolamine
- the amount of the photoinitiating aid is preferably in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 3% by weight, based on the entire photocurable resin composition.
- the photocurable resin composition of the present invention includes various additives, for example, stabilizers (for example, polymerization inhibitors such as hydroquinone, methoquinone, and methylhydroquinone), pigments (for example, cyanine blue, disazo yellow, carmine 6b, Various additives such as colorants such as Raked C, carbon black, and titanium white), fillers, viscosity modifiers, and the like can be contained depending on the purpose.
- the amount of the stabilizer contained in the photocurable resin composition is preferably in the range of 0.01 to 2% by weight, preferably 0.1 to 1% by weight, based on the entire photocurable resin composition. A range is more preferred.
- the amount of the colorant is preferably in the range of 1 to 50% by weight and more preferably in the range of 1 to 45% by weight with respect to the entire photocurable resin composition.
- the photocurable resin composition of the present invention comprises, in the polymer (A), an ethylenically unsaturated compound (B), if necessary, a photopolymerization initiator, a photoinitiator auxiliary, an additive (for example, It can be produced by mixing stabilizers and pigments.
- the photocurable resin composition of the present invention is cured by irradiating light.
- the light used for curing is generally ultraviolet light.
- the curing device used for the curing reaction of the photocurable resin composition and the curing conditions are not particularly limited, and any method may be used as long as it is a normal photocuring reaction.
- the use of the photocurable resin composition of the present invention is not particularly limited. Inks (for example, printing inks for photo-curable lithographic printing plates, silk screen inks, gravure inks, etc.), paints (for example, paints for paper, plastics, metals, woodworking, for example, overprint varnishes) ), Adhesives, photoresists, and other technical fields.
- the ink containing the photocurable resin composition of the present invention is the ink of the present invention, and the paint containing the photocurable resin composition of the present invention is the paint of the present invention.
- the coating material of this invention is an overprint varnish.
- a general method for producing ink is as follows.
- the polymer (A), the stabilizer and the like are dissolved in the ethylenically unsaturated compound (B) at a temperature of 60 ° C. to 100 ° C. with stirring to prepare a varnish.
- the ink is obtained by mixing the varnish with a pigment, a photopolymerization initiator, and other additives with a butterfly mixer and then kneading with a three-roll roll.
- the overprint varnish can be prepared by the same procedure as that for ink except that no pigment is used.
- Weight average molecular weight (Mw) and Molecular Weight Distribution (Mw / Mn) of Polymer were measured using GPC.
- Mw and Mn are values of weight average molecular weight and number average molecular weight in terms of standard polystyrene.
- Components other than the polymers 1 to 3 shown in Table 1 are as follows. The composition amounts shown in Table 1 are expressed in parts by weight.
- DAP resin Daisodap A (diallyl phthalate resin) manufactured by Osaka Soda Co., Ltd.
- Triallyl isocyanurate (monomer) DTMPTA Sartomer Co., Ltd.
- Irgacure 907 BASF Japan K.K. 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
- Irganox 1076 BASF Japan K.K.
- Table 1 shows the polymers 1 to 3, the DAP resin, triallyl isocyanurate (monomer), the ethylenic compound, and the polymerization initiator obtained in each production example. Each described composition amount was added and mixed by heating to prepare a photocurable resin composition. After each composition was cooled to room temperature (25 ° C.), solubility was confirmed by checking whether the appearance of the composition after one night was transparent. The one whose appearance was transparent even after cooling was rated as ⁇ , and the one that became cloudy was marked as x. The results are shown in Table 2.
- the photocurable resin composition prepared using the polymers 1 to 3 obtained by polymerizing the compound represented by the general formula [I] is shown in Comparative Example 1. It has a drying property equivalent to that of a photocurable resin composition prepared using such a DAP resin. And it is excellent also in the adhesiveness to a polypropylene sheet with which adhesion is difficult with the photocurable resin composition of the comparative example 1 prepared using the DAP resin, and the comparative example 2 adjusted using the triallyl isocyanurate (monomer).
- the photo-curable resin composition of the present invention can be used for inks for plastic substrates (for example, offset inks), paints, adhesives, photoresists, and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
下記一般式[I]で表される化合物を重合して得られる重合体(A)を含有することを特徴とする。
また、この光硬化性樹脂組成物は特にPP(ポリプロピレン)樹脂に対する密着性に優れるため、従来のジアリルフタレート樹脂を用いた組成物では密着性を高くすることが困難であったPP樹脂用のインキ、塗料の成分として適している。
このインキは、プラスチック基材に印刷するためのインキとして適しており、特にPP樹脂製のシート、フィルム等の基材に印刷するためのインキとして適している。
この塗料は、プラスチック基材に描画するための塗料として適しており、特にPP樹脂製のシート、フィルム等の基材に描画するための塗料として適している。
また、本発明の塗料はオーバープリントワニスであることが好ましい。
本発明の光硬化性樹脂組成物は、下記一般式[I]で表される化合物を重合して得られる重合体(A)を含有することを特徴とする。
本発明において、重合体(A)を含有することにより、合成高分子の基材、特にプラスチック基材に対する密着性に優れる理由については定かではないが、以下のように推測される。
下記一般式[I]で表される化合物を重合して得られる重合体(A)では、イソシアヌレート環に基づく構造(下記一般式[I]中の環構造(イソシアネートの三量体))が連続して存在しており、連続して存在するイソシアヌレート環に基づく構造により、合成高分子の基材、特にプラスチック基材に対する密着性に優れるものと推測される。
本明細書において、重合体(A)の重量平均分子量(Mw)、数平均分子量(Mn)は実施例に記載の方法により測定される値である。
本発明の光硬化性樹脂組成物は、光照射により硬化可能であるエチレン性不飽和化合物(B)を含有することが好ましい。エチレン性不飽和化合物(B)は、炭素-炭素二重結合を1~20個有することが好ましく、1~10個有することがより好ましく、2~6個有することがさらに好ましい。エチレン性不飽和化合物(B)としては、(メタ)アクリル酸エステル化合物、(メタ)アリル化合物及びビニル化合物等が挙げられる。また、エチレン性不飽和化合物は2種以上の化合物の混合物を用いることも可能である。
ビニル化合物としては、スチレン、ジビニルベンゼン、N-ビニルピロリドン、酢酸ビニル等を例示することができる。
また、本発明の光硬化性樹脂組成物中における重合体(A)とエチレン性不飽和化合物(B)の比率(重合体:エチレン性不飽和化合物)は、重量比で、5:95~95:5の範囲であればよく、10:90~90:10の範囲であることが好ましく、10:90~70:30の範囲であることがより好ましく、10:90~50:50の範囲であることがさらに好ましい。上記範囲内であれば、プラスチック基材への充分な密着性が得られやすい。
本発明の光硬化性樹脂組成物は、重合開始剤を含んでいてもよく、特に光重合開始剤を含有することが好ましい。光硬化性樹脂組成物に含有される光重合開始剤としては、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、等のアセトフェノン系、ベンゾイン、ベンゾインエチルエ-テル等のベンゾイン系、ベンゾフェノン等のベンゾフェノン系、アシルフォスフィンオキサイド等のリン系、チオキサントン等のイオウ系、ベンジル、9,10-フェナンスレンキノン等のベンジル系が挙げられる。
光開始助剤の量は、光硬化性樹脂組成物全体に対して、0.1~5重量%の範囲であることが好ましく、0.5~3重量%の範囲がより好ましい。
着色剤の量は、光硬化性樹脂組成物全体に対して、1~50重量%の範囲であることが好ましく、1~45重量%の範囲がより好ましい。
本発明の光硬化性樹脂組成物を含むインキは本発明のインキであり、本発明の光硬化性樹脂組成物を含む塗料は本発明の塗料である。また、本発明の塗料はオーバープリントワニスであることが好ましい。
また、オーバープリントワニスの作成は、顔料を使用しない以外は、インキと同様の手順により行える。
以下、実施例を挙げて、本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
カラム:ShodexLF-804×2本を直列に接続
流速:1.0mL/min
温度:40℃
検出:RID-20A
試料:試料30mgをテトラヒドロフラン3mLに溶解させ測定用のサンプルとした。
3Lのセパラブルフラスコにトリアリルイソシアヌレート600gを加え、15gのベンゾイルパーオキサイドを加えて80℃で加熱攪拌した。1時間反応させた後、室温(25℃)まで冷却した。冷却後、フラスコにメタノールを加え、重合体を沈殿させた。得られた重合体を40℃で16時間減圧乾燥した(収量:73g、収率:12%、Mw=53,000、Mw/Mn=3.3)。得られた重合体を重合体1とし、実施例1、4~6に用いた。
製造例1の反応時間を1.25時間とした以外は同様の方法で合成を行った。(収量:84g、収率:14%、Mw=94,000、Mw/Mn=5.3)。得られた重合体を重合体2とし、実施例2に用いた。
製造例1の反応時間を1.5時間とした以外は同様の方法で合成を行った。(収量:94g、収率:16%、Mw=126,000、Mw/Mn=6.9)。得られた重合体を重合体3とし、実施例3に用いた。
下記表1に記載の各組成の光硬化性樹脂組成物を調製し、光硬化性樹脂組成物の特性を評価した。
また、表1に示す組成量は重量部での表記である。
DAP樹脂:(株)大阪ソーダ製 ダイソーダップA(ジアリルフタレート樹脂)
トリアリルイソシアヌレート(モノマー)
DTMPTA:サートマー(株)製 SR355 ジトリメチロールプロパンテトラアクリレート
Irgacure907:BASF ジャパン(株)製 2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン
Irganox1076:BASFジャパン(株)製 オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート
各製造例で得られた各重合体1~3、DAP樹脂、トリアリルイソシアヌレート(モノマー)、エチレン性化合物、及び重合開始剤を表1に記載した各組成量を添加し、加熱混合して光硬化性樹脂組成物を調製した。各組成物を室温(25℃)に冷却後、一晩経過したものの外観が透明であるかで溶解性を確認した。冷却後も外観が透明であったものを〇、白濁したものを×とした。結果は表2に示す。
調製した光硬化性樹脂組成物を、プラスチックフィルム(ポリプロピレン基材:龍田化学株式会社製 無延伸高透明PPシート 品名:ハイピークリスタル ST-500 厚み0.3mm)にRIテスターを用いてコートし、出力120W/cmのメタルハライドランプ(ランプ距離11cm、コンベアスピード50m/min)で硬化させた。なお、UV硬化装置はアイグラフィックス株式会社製コンベア型紫外線硬化装置を用いた。塗膜を指で触り、面に指紋が付かない状態(タックフリー)になるまで複数回通過させ、その回数で乾燥性を評価した。評価結果を表2に示す。
調製した光硬化性樹脂組成物を、乾燥性試験と同様の方法でプラスチックフィルムにコートし、硬化させた。得られた塗膜に、ニチバン社製18mm幅のセロテープ(登録商標、品番:LP-18、粘着力:4.01N/10mm)を貼り付け、親指で10回強く擦った後、セロテープ(登録商標)を真上にゆっくりと引き離した。完全に剥離しなかったものを○、完全に剥離したものを×とした。評価結果を表2に示す。
Claims (6)
- 更に、エチレン性不飽和化合物(B)を含有することを特徴とする請求項1に記載の光硬化性樹脂組成物。
- 更に、光重合開始剤を含有する請求項1又は2に記載の光硬化性樹脂組成物。
- 請求項1~3の何れかに記載の光硬化性樹脂組成物を含むことを特徴とするインキ。
- 請求項1~3の何れかに記載の光硬化性樹脂組成物を含むことを特徴とする塗料。
- オーバープリントワニスである請求項5に記載の塗料。
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EP17843397.5A EP3502150A4 (en) | 2016-08-22 | 2017-08-08 | PHOTOSETTING RESIN COMPOSITION, INK AND COATING MATERIAL |
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US11149157B2 (en) | 2021-10-19 |
CN109641985A (zh) | 2019-04-16 |
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EP3502150A1 (en) | 2019-06-26 |
TWI808944B (zh) | 2023-07-21 |
CN109641985B (zh) | 2022-04-22 |
EP3502150A4 (en) | 2020-01-22 |
US20190203061A1 (en) | 2019-07-04 |
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JPWO2018037912A1 (ja) | 2019-06-20 |
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