WO2014156454A1 - Composition de résine durcissable par rayonnement d'énergie active et article durci faite de celle-ci - Google Patents

Composition de résine durcissable par rayonnement d'énergie active et article durci faite de celle-ci Download PDF

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WO2014156454A1
WO2014156454A1 PCT/JP2014/054855 JP2014054855W WO2014156454A1 WO 2014156454 A1 WO2014156454 A1 WO 2014156454A1 JP 2014054855 W JP2014054855 W JP 2014054855W WO 2014156454 A1 WO2014156454 A1 WO 2014156454A1
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double bond
active energy
energy ray
acrylate
meth
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PCT/JP2014/054855
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English (en)
Japanese (ja)
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昇平 槇田
千弘 舟越
峰岸　昌司
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太陽インキ製造株式会社
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Priority to CN201480005395.2A priority Critical patent/CN104937000B/zh
Priority to KR1020157021820A priority patent/KR20150135221A/ko
Priority to JP2015508201A priority patent/JP6232049B2/ja
Publication of WO2014156454A1 publication Critical patent/WO2014156454A1/fr

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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to an active energy ray-curable resin composition useful for applications such as mobile phone buttons that require low warpage, adhesion under high temperature and high humidity, and wear resistance.
  • active energy ray-curable resins that are cured by active energy rays such as ultraviolet rays and electron beams have been used in various applications.
  • active energy ray-curable resins used for mobile phone buttons and the like generally require characteristics such as transparency and low curing shrinkage.
  • high reliability that does not cause problems even under high temperature and high humidity is required.
  • an active energy ray curable resin composition containing a bifunctional urethane (meth) acrylate resin, isoboronyl (meth) acrylate and a photopolymerization initiator (Patent Document 1)
  • An active energy ray-curable resin composition (Patent Document 2) containing a bifunctional urethane (meth) acrylate resin, a bifunctional or trifunctional (meth) acrylate to which an alkylene oxide is added, and a photopolymerization initiator has been proposed.
  • the active energy ray-curable resin composition described in Patent Document 3 has a high balance between low cure shrinkage, wear resistance, and impact resistance.
  • secondary processing may be required to further shape the obtained laminate.
  • exfoliation, peeling, etc. may be seen in the film
  • the object of the present invention is to exhibit high adhesion and excellent wear resistance even under high temperature and high humidity with little warping when cured by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • Another object of the present invention is to provide an active energy ray-curable resin composition that is also excellent in secondary processability such as molding after curing.
  • an object of the present invention is to provide a cured product obtained by curing the active energy ray-curable resin composition.
  • the purpose is (A) a resin having a plurality of acrylate groups or methacrylate groups, (B) at least one selected from amides having an ethylenic double bond and amide derivatives; (C) at least one selected from a bifunctional acrylate and a bifunctional methacrylate having a cyclic skeleton not containing a carbon-carbon double bond, (D) a photopolymerization initiator, and (E) a polymer containing no ethylenic double bond, and (E) the polymer containing no ethylenic double bond has the (B) ethylenic double bond. It can be achieved by an active energy ray-curable composition that is soluble in at least one selected from amides and amide derivatives.
  • the above “the polymer not containing the ethylenic double bond is dissolved in at least one selected from the amide having the ethylenic double bond and the amide derivative” does not contain the ethylenic double bond.
  • 10 parts by mass of the polymer can be dissolved at 80 ° C. or less in 90 parts by mass of at least one monomer (preferably N-acryloylmorpholine) selected from amides having an ethylenic double bond and amide derivatives (polymer) 10 mass% monomer solution can be prepared at 80 ° C. or lower).
  • 10 g of the polymer is added to 90 g of the monomer, heated to 80 ° C., then stirred for 10 minutes, and then judged by observing whether or not it has dissolved.
  • the polymer (E) containing no ethylenic double bond is a thermoplastic resin, particularly a polymer having a polar group (preferably a thermoplastic resin).
  • the polar group include an ester group (bond), an ether group (bond), a hydroxyl group, and a urethane group (bond). Generally, these groups are included in the repeating unit of the polymer.
  • the polymer containing no (E) ethylenic double bond is preferably contained in an amount of 1 to 10 parts by weight, particularly 2 to 7 parts by weight, based on 100 parts by weight of the resin (A).
  • the amide having an ethylenic double bond or the derivative is N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N-acryloylmorpholine, N-methacryloyl Consists of at least one morpholine.
  • the cured product (molded product) of the present invention can be obtained by curing the above active energy ray-curable resin composition.
  • the ethylenic double bond in the present invention means a carbon-carbon double bond present at the molecular end.
  • the curable composition of the present invention When the curable composition of the present invention is cured by irradiation with active energy rays, the obtained cured product hardly causes warpage, exhibits high adhesion and excellent wear resistance even under high temperature and high humidity, Furthermore, it is excellent in secondary workability such as molding after curing. That is, the cured product of the curable composition of the present invention has a low level of warpage, adhesion, and wear resistance at a high level by a cured material having an ethylenic double bond. In addition to these properties, high toughness is obtained by the addition of a polymer that does not contain an ionic double bond, that is, is not cured by irradiation with active energy rays.
  • the cured product of the curable composition of the present invention is excellent in secondary workability.
  • FIG. 1 shows an example of a mold having a concave portion on the surface used for producing the cured product of the present invention.
  • FIG. 2 shows a state in which the concave portion of the mold is filled with the active energy ray resin composition of the present invention.
  • FIG. 3 shows a state in which the active energy rays are irradiated from above the base material placed on the mold and the composition.
  • FIG. 4 shows a state in which the obtained laminate of the base material and the cured product of the composition is released from the mold.
  • FIG. 5 shows a state in which a laminate of a base material and a cured product of the curable resin composition is placed on one mold.
  • FIG. 6 shows a state where a pair of molds are pressed from above the laminate.
  • FIG. 7 shows a molded body taken out from the mold.
  • the resin having a plurality of (meth) acrylate groups contained in the active energy ray-curable resin composition of the present invention preferably has a weight average molecular weight in the range of 1,000 to 20,000.
  • the weight average molecular weight is less than 1,000, the crosslink density of a cured product obtained by a resin having a plurality of (meth) acrylate groups increases, and the curing shrinkage of the resin also increases, so that the warpage of the cured product also increases.
  • the weight average molecular weight exceeds 20,000, the viscosity becomes high and it cannot be used in the application of the present invention.
  • (meth) acrylate is a term generically referring to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
  • Examples of the resin (A) having a plurality of (meth) acrylate groups include urethane resins, polyester resins, epoxy resins, and acrylic resins having a plurality of (meth) acrylate groups. Since low warpage, adhesion, and abrasion resistance can be obtained at a high level, the resin having a plurality of (meth) acrylate groups is preferably a urethane resin.
  • urethane resins examples include U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, and UA-340P manufactured by Shin-Nakamura Chemical Co., Ltd. UA-2235PE, UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100; CN962, CN963, CN964, CN965, CN980, CN981, CN982, CN983 manufactured by Sartomer Co., Ltd.
  • CN929, CN944B85, CN989, CN9008 manufactured by Sartomer Co., Ltd .; Etc.
  • Shin-Nakamura Chemical Co., Ltd. U-6HA, U-6H, U-15HA, UA-32P, U-324A, UA-7200; Sartomer Co., Ltd. CN968, CN9006, CN9010; UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN-952 manufactured by Kogyo Co., Ltd. 1290K, KRM8200, Evecril 5129, Evekril 8210, Evekril 8301, Evekril 8405 and the like.
  • urethane resins having a plurality of (meth) acrylate groups may be used alone or in admixture of two or more.
  • Examples of (B) an amide having an ethylenic double bond and an amide derivative contained in the active energy ray-curable resin composition of the present invention include N-vinylformamide, N-vinylacetamide, (meth) acrylamide, N- Methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N- n-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-tetrahydrofurfuryl (meth) acrylamide, N-ethoxypropyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N- 1-methyl-2
  • a photosensitive amide compound having a (meth) acryloyl group is preferable, and in particular, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N-acryloylmorpholine, and N-methacryloylmorpholine are transparent. It is preferable from the point.
  • At least one selected from (B) an amide having an ethylenic double bond and an amide derivative is 15 to 200 with respect to 100 parts by mass of (A) a resin having a plurality of (meth) acrylate groups. It is preferably contained in a proportion of 20 parts by mass, more preferably 20-100 parts by mass. (B) When the blending amount of at least one selected from amides having an ethylenic double bond and amide derivatives is less than 15 parts by mass, the adhesiveness of the cured product may be insufficient, while 200 masses. If it exceeds the part, the brittleness of the cured product may become remarkable, which is not preferable.
  • the bifunctional (meth) acrylate having a cyclic skeleton that does not contain a carbon-carbon double bond contained in the active energy ray-curable resin composition of the present invention prevents warping by not containing a double bond.
  • wear resistance can be enhanced by having an annular skeleton.
  • the weight average molecular weight is preferably in the range of 150 to 2,000.
  • the weight average molecular weight is less than 150, the crosslink density provided between the urethane resin having a plurality of (meth) acrylate groups is increased, and the cure shrinkage of the resin is increased, so that the warpage of the cured molded product is also increased.
  • the weight average molecular weight exceeds 2,000, the viscosity becomes high and workability is lowered, which is not preferable.
  • Examples of the (C) bifunctional (meth) acrylate having a cyclic skeleton having no carbon-carbon double bond include cyclohexanedimethanol di (meth) acrylate, tricyclodencandimethanol di (meth) acrylate, hydrogen Alicyclic skeletons such as hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated hexafluorobisphenol A di (meth) acrylate, bis (2- (meth) acryloyloxy) hexahydrophthalic acid Difunctional (meth) acrylate having 5-ethyl-2- (2-hydroxy-1,1dimethylethyl) -5- (hydroxymethyl) -1,3-dioxane diacrylate, 1,4-di (meth) Bifunctional (meth) acrylates having a heterocyclic skeleton such as acryloylpiperazine ; More thereof may be used bifunctional (meth)
  • Such (C) bifunctional (meth) acrylate having a cyclic skeleton having no carbon-carbon double bond is 5 to 100 masses per 100 mass parts of urethane resin having a plurality of (meth) acrylate groups. Part, and preferably 10 to 50 parts by mass.
  • Examples of the (D) photopolymerization initiator contained in the active energy ray-curable resin composition of the present invention include benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin.
  • benzoins such as n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone; acetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone Acetophenones such as 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and N, N-dimethylaminoacetophenone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro Thioxanthones such as thioxanthone and 2,4-d
  • Anthraquinones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p- Benzoic acid esters such as dimethyl benzoic acid ethyl ester; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like.
  • This (D) photopolymerization initiator can be used alone or in combination of two or more.
  • This (D) photopolymerization initiator is contained in a proportion of 0.1 to 10 parts by mass, and further 0.3 to 5 parts by mass with respect to 100 parts by mass of the resin (A) having a plurality of (meth) acrylate groups. It is preferable that
  • the active energy ray-curable resin composition of the present invention further includes (E) a polymer that does not contain an ethylenic double bond.
  • the polymer containing no ethylenic double bond may be any polymer as long as it does not contain an ethylenic double bond, and may be a thermoplastic resin or a thermosetting resin. Is preferred.
  • the polymer which does not contain an ethylenic double bond of the present invention needs to be dissolved in at least one selected from amides having an ethylenic double bond and amide derivatives.
  • the above (E) polymer containing no ethylenic double bond is preferably a polymer having a polar group (thermoplastic resin).
  • a polymer is preferable because it is easily dissolved in a bifunctional acrylate and a bifunctional methacrylate and is excellent in compatibility with other components.
  • polar groups include ester groups (bonds), ether groups (bonds), hydroxyl groups, and urethane groups (bonds).
  • an ester group (bond), an ether group (bond), and a hydroxyl group are preferable.
  • these groups are included in the repeating unit of the polymer (preferably 50% or more of the repeating unit).
  • polymer having such a polar group examples include ethylene / vinyl acetate copolymer, polyvinyl acetal (eg, polyvinyl formal, polyvinyl butyral), polyacetal, acrylic resin (eg, (meth) acrylate homopolymer, (meth) acrylate.
  • polyvinyl acetal eg, polyvinyl formal, polyvinyl butyral
  • acrylic resin eg, (meth) acrylate homopolymer, (meth) acrylate.
  • Copolymer (meth) acrylate block copolymer, (meth) acrylate / styrene copolymer), cellulose resin (eg, cellulose nitrate, cellulose acetate, cellulose propionate, ethyl cellulose), phenoxy resin, polyester resin (eg, , Polyethylene terephthalate, polybutylene terephthalate), polyalkylene oxide (eg, polyethylene oxide, polypropylene oxide), polyurethane, and polyvinyl isobutyl ether.
  • acrylic resin, polyvinyl acetal, cellulose resin, phenoxy resin, and polyester resin are preferable.
  • Preferred acrylic resins include (meth) acrylic acid esters having an alcohol residue of 1 to 10 carbon atoms (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl).
  • a small amount of (meth) acrylate, (meth) acrylamide or the like having a polar group such as a hydroxy group, an amino group or a carboxylic acid group can also be used.
  • copolymers of the above monomers and block copolymers are preferred.
  • PMMA-b-PBA-b-PMMA block
  • Preferred polyvinyl acetals include polyvinyl formal and polyvinyl butyral, with polyvinyl butyral being particularly preferred.
  • Preferred cellulose resins include cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and ethyl cellulose.
  • cellulose acetate propionate cellulose acetate propionate
  • Preferable commercially available products of these polymers include, for example, ESREC BL-1H (produced by Sekisui Chemical Co., Ltd.) as polyvinyl butyral, and CAP504-0.2 (produced by Eastman Chemical Co., Ltd.) as cellulose acetate propionate which is a cellulose resin. ), A block copolymer of acrylic monomers which are acrylic resins, Nano Strength M53 (manufactured by Arkema), PKHB (manufactured by Inchem) as a phenoxy resin, Byron 220 (manufactured by Toyobo Co., Ltd.) as a polyester resin, and the like. it can.
  • the polymer containing no (E) ethylenic double bond and having excellent compatibility with the components other than the polymer containing no (E) ethylenic double bond of the cured composition of the present invention is the curable product of the present invention.
  • Extensibility and toughness can be imparted to the cured product of the composition. For this reason, even when the film of the curable resin composition is formed on a film and the obtained laminate is further molded, occurrence of cracking or peeling of the film of the curable resin composition at the time of molding or after molding. can not see. Therefore, it was confirmed that the hardened
  • the polymer containing no (E) ethylenic double bond of the present invention has a number average molecular weight of 1,000 to 100,000 from the viewpoint of ensuring compatibility with the other components of the cured composition of the present invention. It is preferably in the range, more preferably in the range of 3,000 to 50,000, and still more preferably in the range of 5,000 to 50,000.
  • the number average molecular weight is less than 1,000, it is difficult to impart extensibility and toughness to the cured product of the curable composition.
  • the number average molecular weight exceeds 100,000, The compatibility may be insufficient.
  • the polymer not containing an ethylenic double bond is contained in an amount of 1 to 10 parts by weight, particularly 2 to 7 parts by weight, based on 100 parts by weight of the urethane resin. Is preferred.
  • the content is less than 1 part by mass, it is difficult to impart extensibility and toughness to the cured product of the curable composition.
  • the content exceeds 10 parts by mass, it is a phase with other components of the cured composition. The solubility may be insufficient.
  • the active energy ray-curable resin composition of the present invention can be blended with an inorganic filler as necessary for the purpose of further improving properties such as adhesion of the cured product, mechanical strength, and linear expansion coefficient.
  • an inorganic filler such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc.
  • Inorganic fillers can be used.
  • the inorganic filler is preferably included in an amount of 10 to 100 parts by mass with respect to 100 parts by mass of the urethane resin.
  • an organic solvent may be blended in order to adjust the viscosity of the composition within a range that does not impair the characteristics.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monoethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, and acetates of the above glycol ethers; ethanol, propanol, ethylene glycol, propylene glycol, etc.
  • Alcohols such as octane and decane
  • petroleum oils such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Such as solvent, and the like. These can be used alone or in combination of two or more.
  • phthalocyanine blue In the active energy ray-curable resin composition of the present invention, known and commonly used phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.
  • Colorants known and conventional photopolymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, known and conventional thickeners such as finely divided silica, organic bentonite and montmorillonite, silicone-based, fluorine-based, high
  • additives such as at least one selected from an antifoaming agent such as a molecular system and a leveling agent, and silane coupling agents such as imidazole, thiazole and triazole can be blended.
  • the active energy ray-curable resin composition of the present invention preferably has a viscosity of 1 to 50 dPa ⁇ s.
  • This viscosity is preferably adjusted in the range of 1 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the urethane resin having a plurality of (meth) acrylate groups. Can be provided.
  • the amount of reactive diluent is 1 part by mass or less, the viscosity is high and workability may be lowered.
  • the amount is 100 parts by mass or more, the crosslinking density of the cured product is lowered and sufficient wear resistance cannot be obtained. This is not preferable.
  • This reactive diluent is used as a component other than the amide having an ethylenic double bond and a derivative of the amide, a bifunctional acrylate having a cyclic skeleton not containing a carbon-carbon double bond, and a bifunctional methacrylate.
  • hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate
  • cyclic skeletons such as isobornyl acrylate, tetrahydrofurfuryl acrylate, N-acryloylmorpholine, and N-vinylpyrrolidinone.
  • Monofunctional photosensitive monomers having; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, etc.
  • Aminoalkyl acrylates hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyl
  • Polyhydric alcohols such as ethyl isocyanurate or polyhydric acrylates such as these ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols
  • Acrylates such as: glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl ether acrylates such as triglycidyl isocyanurate; and melamine acrylate, and methacrylates corresponding to the acrylate, etc. Can be mentioned at least one kind. Among these, a
  • the active energy ray-curable resin composition according to the present invention is cured by irradiating active energy rays after being applied to a substrate or the like by the following application method.
  • the cured product or molded product preferably has a durometer hardness D type of 75 ° or more from the viewpoint of warpage prevention.
  • any method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, a gravure printing method, and an offset printing method can be applied.
  • Activating energy rays generally mean ultraviolet rays and electron beams.
  • the ultraviolet irradiation light source a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.
  • a laser beam in the ultraviolet region can also be used.
  • the active energy ray-curable resin composition of the present invention is filled in an intaglio, the filled resin composition is cured with active energy rays, and then the obtained cured product is taken out from the recess to obtain a molded product. it can.
  • a mold 1 having a recess 2 formed on the surface is prepared.
  • a metal such as stainless steel is generally used.
  • the concave portion 2 of the mold 1 is filled with the active energy ray-curable resin composition 3 of the present invention.
  • the filling of the active energy ray-curable resin composition 3 into the concave portion 2 of the mold 1 is generally performed using a doctor knife or the like.
  • the base material 4 is mounted on the surface of the active energy ray curable resin composition 3, and the base material 4 is irradiated with ultraviolet rays from the light source 5 above the active energy ray curable resin composition.
  • the composition is cured.
  • a transparent polyethylene terephthalate or polycarbonate film that transmits ultraviolet rays is used as the substrate.
  • the laminate 6 of the base material 4 and the cured product of the resin composition 3 is released from the mold 1 to obtain a molded product.
  • the series of steps shown in FIGS. 1 to 4 can produce a molded article continuously by using a dedicated apparatus.
  • the obtained molded body uses the active energy ray-curable resin composition 3 of the present invention, there is no warping, the surface has good killing and abrasion properties, and the cured product has good adhesion to the substrate. It is excellent.
  • the elongation of the cured product of the present invention is preferably 5% or more, particularly 7% or more, according to the test method described in the examples.
  • the laminated body 16 of the base material 14 and the cured product 13 of the active energy ray-curable resin composition is placed on a mold 11A, and heated on the pair of molds 11B from above. Pressing (FIG. 6), the resulting molded body 17 is taken out (FIG. 7).
  • the pressing is preferably performed at 100 ° C. to 200 ° C. for several seconds to several minutes. For example, when a PET film is used, it is necessary to perform the treatment at 180 ° C. for several seconds.
  • the cured product 13 of the active energy ray-curable resin composition uses the active energy ray-curable resin composition of the present invention, the cured product 13 maintains the adhesion to the substrate even in the secondary processing described above. At the same time, since the toughness is also obtained, the cured product 13 is not cracked or peeled off from the substrate.
  • the cured product obtained from the curable composition of the present invention exhibits high adhesion and excellent wear resistance under high temperature and high humidity without warping. It can be said that it is excellent also in the next workability.
  • a cured product of the present invention is particularly useful in the field of molded products that require the above characteristics, such as buttons for mobile phones and various cases.
  • the curable composition of this invention is useful for uses, such as UV molding material, the material for optical modeling, and the material for 3D inkjet.
  • the weight average molecular weight and the number average molecular weight of the present invention are measured using standard polystyrene by gel permeation chromatography (GPC).
  • Examples 1 to 7 and Comparative Examples 1 to 6 Preparation of active energy ray-curable resin composition
  • the components shown in Tables 1 and 2 were blended in the resins prepared as described above in the compositions shown in the same table, and stirred and dissolved at 80 ° C. to prepare active energy ray-curable resin compositions.
  • EBECRYL 8807 Aliphatic bifunctional urethane acrylate (manufactured by Daicel-Cytec)
  • KAYARAD RM-1001 N-acryloylmorpholine (manufactured by Nippon Kayaku Co., Ltd.)
  • Light acrylate IB-XA Isoboronyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
  • Aronix M-5700 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Toagosei Co., Ltd.)
  • NK ester A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • CD406 Cyclohexanedimethanol diacrylate (manufactured by Sartomer Co., Ltd.)
  • Neomer BA-641 Ethylene oxide 4 mol addition bisphenol A type diacrylate (manufactured
  • the active energy ray-curable resin composition thus prepared was evaluated for adhesion, warpage, RCA wear, elongation, and moldability during photomolding (presence of cracks) by the following evaluation methods. The results are shown in Table 2.
  • the resin composition is poured into a 2 cm long, 2 cm wide, 1 mm deep Teflon (registered trademark) mold, which is covered with an easy-adhesion-treated PET film, and a UV conveyor furnace (metal halide lamp, 80 W, 3 lights). It was exposed with an integrated light quantity of 1000 mJ / cm 2 and released to obtain a cured coating film.
  • Teflon registered trademark
  • Warp test Place the cured coating film produced by the above method on a flat base so that the warped side faces upward, press one side with the warp against the base with your finger, and lift it from the base on the opposite side. The height was read and the warpage was measured.
  • ⁇ Warpage of cured coating film is less than 5 mm
  • Curing of cured coating film is 5 mm or more and less than 10 mm
  • Curing of cured coating film is 10 mm or more
  • Test method Method for preparing cured product for adhesion and RCA abrasion test
  • the resin composition is applied to easily-adhesion-treated PET with a thickness of 50 ⁇ m using a bar coater, covered with untreated PET from above, and an exposure amount of 1000 mJ / using a UV conveyor furnace (high pressure mercury lamp, 80 W, 3 lamps). It exposed at cm ⁇ 2 > and peeled untreated PET and obtained the cured coating film.
  • RCA wear test The cured coating film produced by the above method was manufactured by NORMAN TOOL, INC. Using an RCA abrasion tester manufactured by Co., Ltd. and a dedicated abrasion paper for RCA abrasion tester, it was worn 50 times under a load of 175 g, and the degree of wear of the cured coating film surface was observed with an optical microscope. ⁇ : Almost no wear ⁇ : Some wear ⁇ : Clear wear
  • Each transparent ultraviolet curable composition was coated on an untreated PET film with a bar coater so that the film thickness after curing was about 100 ⁇ m, and further covered with an untreated PET film from above, and a UV conveyor furnace (high pressure mercury lamp, 80W, 3 lamps) was used for exposure at an exposure amount of 1000 mJ / cm 2 , and the untreated PET film was peeled off to obtain a test piece.
  • a UV conveyor furnace high pressure mercury lamp, 80W, 3 lamps
  • each liquid resin composition under the conditions of a laser power of 100 mW on the irradiated surface (liquid surface) and a scanning speed where the curing depth is 0.2 mm in each composition.
  • a cylindrical molded body having a diameter of 1 cm and a height of 1 cm was manufactured by repeating the process of selectively irradiating a product with laser light to form a cured resin layer (thickness: 0.10 mm).
  • Examples 1 to 7 are excellent in any of the characteristics of warpage, adhesion, wear resistance, elongation, and moldability.
  • Comparative Examples 1 and 2 having the same composition as in the Examples except that the polymer does not contain an ethylenic double bond does not show sufficient performance only in elongation.
  • Comparative Examples 1 and 2 since no polymer containing no ethylenic double bond is included, it is considered that sufficient elongation was not obtained because the toughness of the film was inferior.
  • Comparative Examples 3 to 6 having different compositions in the curing component also have two or more performances of warpage, adhesion, wear resistance, and elongation. It is insufficient.
  • Comparative Example 3 contains at least one selected from a photosensitive amide and a derivative of the photosensitive amide, and thus has good adhesion, but has a bifunctional (meta) having a cyclic skeleton that does not contain a double bond. ) Since it does not contain acrylate, it is inferior in wear resistance and has a problem of warpage.
  • Comparative Example 4 does not contain at least one selected from a photosensitive amide and a derivative of a photosensitive amide and a bifunctional (meth) acrylate having a cyclic skeleton that does not include a double bond, almost all of the properties are inferior. It was. Comparative Example 5 does not contain at least one selected from photosensitive amides and derivatives of photosensitive amides, but has high adhesion because it contains a photosensitive monomer having a hydroxyl group that is a polar group, but contains a double bond. Since it does not contain a bifunctional (meth) acrylate having a cyclic skeleton, the wear resistance is inferior and there is a problem with warpage.
  • Comparative Example 6 had good warpage and adhesion, but was inferior in wear resistance because the bifunctional (meth) acrylate having a cyclic skeleton contained double bonds. Regarding moldability, cracks were observed in Comparative Examples 1 to 6 that did not contain a polymer containing no ethylenic double bond, whereas no cracks were observed in Examples 1 to 7.
  • the curable composition of the present invention can be used for applications such as UV molding material, stereolithography material, 3D inkjet material, and the cured product is particularly useful for mobile phone buttons, various cases, etc. is there.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne une composition de résine durcissable par rayonnement d'énergie active qui présente une adhésivité étroite élevée et une excellente résistance à l'usure même à haute température et humidité élevée sans pratiquement aucun gauchissement lorsqu'elle est durcie par des rayons ultraviolets, un faisceau d'électrons ou un autre rayonnement d'énergie active, et qui présente une aptitude au traitement secondaire comme un moulage excellent après durcissement. Cette composition de résine durcissable par rayonnement d'énergie active se caractérise en ce qu'elle contient : une résine d'uréthane comprenant une pluralité de groupes acrylate ou de groupes méthacrylate ; au moins un amide ou dérivé d'amide choisi parmi ceux comprenant une double liaison éthylénique ; au moins un acrylate bifonctionnel ou méthacrylate bifonctionnel choisi parmi ceux ayant un squelette cyclique ne contenant pas de double liaison carbone-carbone ; un initiateur de photopolymérisation ; et un polymère ne contenant pas de double liaison éthylénique. Cette composition de résine durcissable par rayonnement d'énergie active se caractérise en outre en ce que le polymère ne contenant pas de double liaison éthylénique se dissout dans au moins un amide ou dérivé d'amide choisi parmi ceux comprenant une double liaison éthylénique.
PCT/JP2014/054855 2013-03-28 2014-02-27 Composition de résine durcissable par rayonnement d'énergie active et article durci faite de celle-ci WO2014156454A1 (fr)

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KR1020157021820A KR20150135221A (ko) 2013-03-28 2014-02-27 활성 에너지선 경화성 수지 조성물 및 그의 경화물
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JP2016147949A (ja) * 2015-02-12 2016-08-18 株式会社日本触媒 熱可塑性樹脂組成物とそれを用いた光学フィルム
JP2019526663A (ja) * 2016-08-16 2019-09-19 アルケマ フランス アクリレート系ネットワーク用の重合誘起相分離組成物

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CN108017747B (zh) * 2016-10-31 2021-03-05 固安鼎材科技有限公司 一种碱溶性树脂聚合物、其制备方法和感光性树脂组合物
CN111471347A (zh) * 2020-05-15 2020-07-31 深圳市国瓷永丰源瓷业有限公司 丝网印刷介质组合物、印刷转印纸及其应用

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JPH09217004A (ja) * 1996-02-09 1997-08-19 Takemoto Oil & Fat Co Ltd 光学的立体造形用光硬化性組成物
JP2000001630A (ja) * 1998-04-16 2000-01-07 Takeda Chem Ind Ltd 光ファイバ被覆用紫外線硬化型樹脂組成物
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JP2016147949A (ja) * 2015-02-12 2016-08-18 株式会社日本触媒 熱可塑性樹脂組成物とそれを用いた光学フィルム
JP2019526663A (ja) * 2016-08-16 2019-09-19 アルケマ フランス アクリレート系ネットワーク用の重合誘起相分離組成物

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CN104937000A (zh) 2015-09-23
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JPWO2014156454A1 (ja) 2017-02-16
JP6232049B2 (ja) 2017-11-15

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