WO2015194487A1 - Composition de résine durcissable par rayonnement d'énergie active, ainsi que produit durci et produit moulé associés - Google Patents

Composition de résine durcissable par rayonnement d'énergie active, ainsi que produit durci et produit moulé associés Download PDF

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Publication number
WO2015194487A1
WO2015194487A1 PCT/JP2015/067091 JP2015067091W WO2015194487A1 WO 2015194487 A1 WO2015194487 A1 WO 2015194487A1 JP 2015067091 W JP2015067091 W JP 2015067091W WO 2015194487 A1 WO2015194487 A1 WO 2015194487A1
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WIPO (PCT)
Prior art keywords
meth
active energy
energy ray
curable resin
resin composition
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PCT/JP2015/067091
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English (en)
Japanese (ja)
Inventor
学 北田
Original Assignee
ポリマテック・ジャパン株式会社
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Publication date
Application filed by ポリマテック・ジャパン株式会社 filed Critical ポリマテック・ジャパン株式会社
Priority to CN201580030336.5A priority Critical patent/CN106459322A/zh
Priority to JP2016529318A priority patent/JPWO2015194487A1/ja
Publication of WO2015194487A1 publication Critical patent/WO2015194487A1/fr

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Classifications

    • 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

Definitions

  • the present invention cures rapidly by irradiation with active energy rays such as ultraviolet rays, and is suitable for producing a cured product excellent in chemical resistance, low warpage, high hardness, and adhesion to a substrate.
  • the present invention relates to a curable resin composition, a cured product obtained by curing the curable resin composition, and a molded body.
  • the cured product obtained from the active energy ray-curable resin composition is known to have excellent properties such as chemical resistance, high hardness, adhesion to the substrate, and toughness. Since it is cured and excellent in transparency, it is a material suitable as a hard material for the thin parts.
  • this active energy ray-curable resin composition for example, an example using a bifunctional acrylate having a cyclic skeleton not containing a double bond as a raw material is described in JP2011-173982A (Patent Document 1). .
  • This active energy ray-curable resin composition can improve the cross-linking density by using a bifunctional acrylate having a cyclic skeleton, and can provide excellent effects such as surface hardness and wear resistance.
  • a bifunctional acrylate having a cyclic skeleton can provide excellent effects such as surface hardness and wear resistance.
  • the addition amount of the bifunctional acrylate is small, if a sufficient amount is added, the shrinkage when cured is large, and if the product is molded integrally with a substrate such as a film, the warpage becomes large. There was a disadvantage that the substrate wavy.
  • characteristics such as surface hardness and chemical resistance, and characteristics such as warpage and adhesion to the substrate when integrally formed with a substrate such as a film are in a trade-off relationship, and it was difficult to satisfy all these characteristics by adjusting the crosslink density by increasing or decreasing the bifunctional acrylate.
  • the present invention has been made in order to eliminate such inconveniences, and is an active energy ray-curable resin composition having excellent chemical resistance, high hardness, low warpage, and excellent adhesion to a substrate. It aims at providing a thing, its hardened
  • the present invention is configured as follows to solve the above problems.
  • Active energy ray-curable resin composition comprising a bifunctional urethane (meth) acrylate oligomer having a polyester skeleton, at least one of acrylamide or a derivative thereof, and a monofunctional (meth) acrylate monomer having a heterocyclic group It is.
  • a tough cured product can be obtained, and since it contains at least one of acrylamide or a derivative thereof, adhesion to substrates such as resins and rubber films Can be increased.
  • the monofunctional (meth) acrylate monomer which has a heterocyclic group is included, the surface hardness of hardened
  • the monofunctional (meth) acrylate monomer having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and trimethylolpropane formal (meth) acrylate.
  • the elements constituting the ring of the heterocyclic group can be only carbon and oxygen. Since the elements constituting the ring of the heterocyclic group are only carbon and oxygen, there is a possibility that an effect of improving chemical resistance by containing oxygen and a toughness based on a flexible skeleton containing oxygen may be obtained. . On the other hand, when elements other than oxygen are included, the toughness and adhesion of the cured product may not be sufficiently obtained.
  • Such a heterocyclic group can be at least one of an oxirane ring, an oxirene ring, an oxetane ring, an oxolane ring, a dioxolane ring, an oxane ring and a dioxane ring.
  • cured material is integrally molded on a base material are provided. Since the cured product obtained by curing the active energy ray-curable resin composition is not only chemical resistance and high hardness, it has less warpage and excellent adhesion to the substrate. The same applies to a molded body integrally formed with a substrate such as a film.
  • a cured product obtained by curing an active energy ray-curable resin composition with an active energy ray and a molded product obtained by integrally molding the cured product on a base material include a key sheet, a presser sheet, and a decorative molded part.
  • a key sheet for example, a key sheet provided with a base sheet, a key top film formed on substantially the entire surface of the base sheet, and a key top body in which the key top film partially protrudes
  • the base sheet include a thin molded product made of a thermoplastic resin or rubber in addition to a resin film, a rubber sheet, a metal sheet, and the like.
  • a cured product excellent in chemical resistance, low warpage, high hardness, and adhesion to a substrate can be produced. According to the molded body, such properties can be provided.
  • the active energy ray-curable resin composition described below includes a bifunctional urethane (meth) acrylate oligomer having a polyester skeleton (component A), at least one of acrylamide and its derivative (component B), and a heterocyclic group. And a monofunctional (meth) acrylate monomer (component C).
  • the bifunctional urethane (meth) acrylate oligomer having a polyester skeleton is a bifunctional oligomer.
  • the reason why it is bifunctional is that the crosslink density becomes too high when it is trifunctional or higher.
  • a tough cured product cannot be obtained.
  • the oligomer preferably has a weight average molecular weight of 1,000 to 20,000. If it is less than 1,000, there exists a possibility that the crosslinking density may become high too much and the curvature of hardened
  • bifunctional urethane (meth) acrylate oligomer various products manufactured by Toa Gosei Co., Ltd., Sartomer, Kyoeisha Chemical Co., etc. can be used. These bifunctional urethane (meth) acrylate oligomers can be used alone or Two or more kinds can be mixed and used.
  • the glass transition temperature (Tg) of the bifunctional urethane (meth) acrylate oligomer having a polyester skeleton is preferably ⁇ 30 ° C. to 60 ° C., and more preferably 20 ° C. to 55 ° C. This is because it is easy to obtain a cured product having substrate adhesion, low warpage, high hardness, and chemical resistance.
  • Tg is less than ⁇ 30 ° C., low warpage is good, but hardness and chemical resistance tend to deteriorate, and when Tg exceeds 60 ° C., low warpage tends to deteriorate.
  • Acrylamide or its derivatives include (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-Nn-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-ethoxypropyl (meth) acrylamide, N-tetrahydrofurfuryl (meta ) Acrylamide, N-ethoxyethyl (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N-morpholinopropyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-isopropoxyethyl (Meth) acrylamide, N-isopropoxy
  • cyclic acrylamides and derivatives thereof such as N-vinylcaprolactam, N-vinylpyrrolidone, N- (meth) acryloylmorpholine and N- (meth) acryloylpiperidine.
  • Preferred is acrylamide or a derivative thereof having a (meth) acryloyl group
  • N-acryloylmorpholine is a particularly preferred acrylamide or one of its derivatives.
  • the amount of acrylamide or its derivative added is preferably 3 to 40% by weight, more preferably 5 to 20% by weight, based on the total solid content. If the addition amount is less than 3% by weight, the adhesion to the substrate tends to be inferior, and if the addition amount is more than 40%, the adhesion to the mold to be cast becomes high and the demolding property tends to deteriorate. It is in.
  • Monofunctional (meth) acrylate monomers having a heterocyclic group include, for example, tetrahydrofurfuryl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidi Nyl (meth) acrylate, (meth) acryloylmorpholine, etc. are mentioned.
  • the elements constituting the ring of the heterocyclic group are only carbon and oxygen, since high chemical resistance can be obtained by giving oxygen to the heterocyclic group.
  • a heterocyclic ring include an oxirane ring, an oxirene ring, an oxetane ring, an oxolane ring, a dioxolane ring, an oxane ring, and a dioxane ring.
  • monofunctional (meth) acrylate monomers having oxygen in the heterocyclic group tetrahydrofurfuryl (meth) acrylate or trimethylolpropane formal (meth) acrylate can provide particularly high chemical resistance. preferable.
  • a cyclic monofunctional (meth) acrylate monomer that is not a heterocyclic group it is a preferred embodiment to mix a cyclic monofunctional (meth) acrylate monomer that is not a heterocyclic group together with a monofunctional (meth) acrylate monomer having a heterocyclic group.
  • a monofunctional (meth) acrylate monomer having a heterocyclic group When the content of the monofunctional (meth) acrylate monomer having a heterocyclic group is reduced, mixing such a cyclic monofunctional (meth) acrylate monomer that is not a heterocyclic group helps to increase chemical resistance and hardness. is there.
  • the cyclic monofunctional (meth) acrylate monomer include isobornyl methacrylate and cyclohexyl methacrylate.
  • the total content of the monofunctional (meth) acrylate monomer having a heterocyclic group and the cyclic monofunctional (meth) acrylate monomer is preferably 35 to 55% by weight based on the total solid content. If it is less than 35% by weight, the hardness is lowered and the chemical resistance may be deteriorated. Moreover, when it exceeds 55 weight%, content of a bifunctional urethane (meth) acrylate oligomer will decrease relatively, the toughness of hardened
  • the photopolymerization initiator benzophenone series, thioxanthone series, acetophenone series, acylphosphine series and the like are used, and examples thereof include IRGACURE (trade name) manufactured by BASF Japan, and one kind of photopolymerization initiator or Two or more kinds can be used in combination.
  • the addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the bifunctional urethane (meth) acrylate oligomer.
  • various diluents, additives, fillers and the like can be added for various purposes.
  • an inorganic filler such as amorphous silica or calcium carbonate
  • properties such as mechanical strength and chemical resistance of the cured product can be improved.
  • a colorant such as phthalocyanine blue, titanium oxide, or carbon black
  • the cured product can be colored.
  • the viscosity of the active energy ray-curable resin composition is preferably 150 to 1500 mPa ⁇ s at 25 ° C.
  • the viscosity is lower than 150 mPa ⁇ s, the material flows out during mold casting, making it difficult to mold.
  • the viscosity is higher than 1500 mPa ⁇ s, casting becomes difficult and a molded product with a desired shape is obtained. It's hard to be done.
  • the active energy ray-curable resin composition can be used by being applied to a substrate made of a resin, an elastomer, or the like, or injected into a mold and bonded to these substrates.
  • Examples of the active energy ray for curing the active energy ray-curable resin composition include ultraviolet rays, electron beams, visible light, infrared light, X-rays, ⁇ rays, ⁇ rays, ⁇ rays, and the like.
  • Examples of the light source for irradiating these include a UV light source, a UV-LED light source, various mercury lamps, sodium lamps, xenon lamps, metal halide lamps, and the like.
  • Active energy ray-curable type containing component A which is a bifunctional urethane acrylate oligomer having a polyester skeleton, component B which is acrylamide or a derivative thereof, and component C which is a monofunctional (meth) acrylate monomer having a heterocyclic group
  • component A which is a bifunctional urethane acrylate oligomer having a polyester skeleton
  • component B which is acrylamide or a derivative thereof
  • component C which is a monofunctional (meth) acrylate monomer having a heterocyclic group
  • CN9009 trade name manufactured by Sartomer.
  • CN9788 trade name manufactured by Sartomer.
  • CN 996 trade name manufactured by Sartomer.
  • CN929 trade name manufactured by Sartomer.
  • Irgacure 184 trade name of BASF Japan.
  • ⁇ Base material adhesion> The adhesion between the substrate and the cured product when each sample was cured on the resin serving as the substrate was tested.
  • (Easy-adhesive PET: 300 ⁇ m thickness) is prepared as a base material, and a sample is filled into a mold from which a cured product having a diameter of 5 mm and a height of 5 mm can be obtained. Then, the sample was solidified by irradiation with active energy rays (ultraviolet rays) under conditions of illuminance: 500 mW / cm 2 and integrated light quantity: 3000 mJ / cm 2 from above easy-adhesion PET.
  • active energy rays ultraviolet rays
  • the adhesion was judged from the ease of peeling when a nail was hooked on the end of the cured product fixed to the easy-adhesion PET on the surface having a diameter of 5 mm and the cured product was peeled off. Those that were not peeled were evaluated as “ ⁇ ”, those that were difficult to peel off were evaluated as “ ⁇ ”, and those that were easily peeled off were evaluated as “ ⁇ ”.
  • ⁇ Chemical resistance> Each sample was irradiated with ultraviolet rays under the conditions of 500 mW / cm 2 and integrated light quantity: 3000 mJ / cm 2 to prepare a cured product having a size of 10 mm ⁇ 50 mm ⁇ 0.5 mm. This cured product was immersed in two kinds of chemicals, and the chemical resistance was evaluated from the degree of swelling obtained by the following formula.
  • -Swelling degree weight after soaking in chemicals / weight before soaking in chemicals
  • oleic acid and ethanol as chemicals, oleic acid at 50 ° C for 24 hours, ethanol at 25 ° C Each was immersed for 24 hours.
  • ⁇ Demoldability> Whether the sample is filled in a mold having a plurality of recesses of 10 mm ⁇ 5 mm ⁇ depth 0.5 mm, and the sample is covered with the easy-adhesion PET and irradiated with ultraviolet rays under the above conditions to solidify the sample. Tested. In the determination of mold release property, “ ⁇ ” indicates that the mold can be easily removed from the mold, and “X” indicates that the mold cannot be easily removed.
  • sample 8 using a bifunctional urethane (meth) acrylate oligomer having a polyether skeleton instead of the bifunctional urethane (meth) acrylate oligomer having a polyester skeleton (component A) has a hardness of 58 and an ethanol swelling degree. was 1.21, and the result was poor hardness and poor chemical resistance.
  • the sample 10 using the trifunctional urethane (meth) acrylate oligomer while having the same polyester skeleton has a warpage of 7.2 mm. The result was an increase in warpage.
  • Sample 6 to which acryloylmorpholine which is acrylamide or a derivative thereof (component B) was not added had a hardness as low as 52, and the substrate adhesion was not very good.
  • the sample 7 which does not contain the monofunctional (meth) acrylate monomer (component C) which has a heterocyclic group had an oleic acid swelling degree of 1.16 and an ethanol swelling degree of 1.18, and was inferior in chemical resistance. .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition de résine durcissable par rayonnement d'énergie active, laquelle est excellente en termes de résistance chimique et d'adhérence à un film substrat, et laquelle présente un degré élevée de dureté tout en présentant de peu de déformations. L'invention concerne également un produit durci et un produit moulé associés.　Cette composition de résine durcissable par rayonnement d'énergie active contient: un oligomère uréthane (méthacrylate) bifonctionnel possédant un squelette polyester; un acrylamide et/ou un dérivé de celui-ci; et un monomère (méthacrylate) monofonctionnel possédant un groupe hétérocyclique.
PCT/JP2015/067091 2014-06-18 2015-06-12 Composition de résine durcissable par rayonnement d'énergie active, ainsi que produit durci et produit moulé associés WO2015194487A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580030336.5A CN106459322A (zh) 2014-06-18 2015-06-12 活性能量线硬化型树脂组合物以及其硬化物和其成形体
JP2016529318A JPWO2015194487A1 (ja) 2014-06-18 2015-06-12 活性エネルギー線硬化型樹脂組成物およびその硬化物並びにその成形体

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JP2014125322 2014-06-18
JP2014-125322 2014-06-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020064522A1 (fr) 2018-09-24 2020-04-02 Basf Se Composition photodurcissable destinée à être utilisée en impression 3d

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110437385B (zh) * 2019-07-09 2022-04-22 湖南昇微新材料有限公司 一种3d打印用光致变色材料及其制备方法及其应用方法
CN110437376B (zh) * 2019-07-09 2022-05-17 湖南昇微新材料有限公司 高精度3d打印热致变色材料及其制备方法及其应用方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63117023A (ja) * 1986-11-05 1988-05-21 Nippon Kayaku Co Ltd 印刷インキ用組成物
JPH10130586A (ja) * 1996-10-30 1998-05-19 Nippon Kayaku Co Ltd 接着剤組成物、硬化物、物品及び接着方法
JP2003268026A (ja) * 2002-03-12 2003-09-25 Teikoku Printing Inks Mfg Co Ltd 紫外線硬化性組成物、紫外線硬化性インキおよび印刷物
JP2005255844A (ja) * 2004-03-11 2005-09-22 Jsr Corp 放射性硬化性組成物
JP2011256307A (ja) * 2010-06-10 2011-12-22 Mitsubishi Rayon Co Ltd 注型用活性エネルギー線硬化性樹脂組成物および光学部品
JP2014141654A (ja) * 2012-12-28 2014-08-07 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化性樹脂組成物及びコーティング剤

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
JP3835857B2 (ja) * 1996-06-18 2006-10-18 日本化薬株式会社 光ディスク用接着剤組成物、硬化物、物品及び接着方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63117023A (ja) * 1986-11-05 1988-05-21 Nippon Kayaku Co Ltd 印刷インキ用組成物
JPH10130586A (ja) * 1996-10-30 1998-05-19 Nippon Kayaku Co Ltd 接着剤組成物、硬化物、物品及び接着方法
JP2003268026A (ja) * 2002-03-12 2003-09-25 Teikoku Printing Inks Mfg Co Ltd 紫外線硬化性組成物、紫外線硬化性インキおよび印刷物
JP2005255844A (ja) * 2004-03-11 2005-09-22 Jsr Corp 放射性硬化性組成物
JP2011256307A (ja) * 2010-06-10 2011-12-22 Mitsubishi Rayon Co Ltd 注型用活性エネルギー線硬化性樹脂組成物および光学部品
JP2014141654A (ja) * 2012-12-28 2014-08-07 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化性樹脂組成物及びコーティング剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020064522A1 (fr) 2018-09-24 2020-04-02 Basf Se Composition photodurcissable destinée à être utilisée en impression 3d

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CN106459322A (zh) 2017-02-22
JPWO2015194487A1 (ja) 2017-05-25

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