WO2020130072A1 - Agent de revêtement, film de revêtement et stratifié - Google Patents

Agent de revêtement, film de revêtement et stratifié Download PDF

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Publication number
WO2020130072A1
WO2020130072A1 PCT/JP2019/049800 JP2019049800W WO2020130072A1 WO 2020130072 A1 WO2020130072 A1 WO 2020130072A1 JP 2019049800 W JP2019049800 W JP 2019049800W WO 2020130072 A1 WO2020130072 A1 WO 2020130072A1
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WO
WIPO (PCT)
Prior art keywords
formula
meth
acrylate
group
represented
Prior art date
Application number
PCT/JP2019/049800
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English (en)
Japanese (ja)
Inventor
賢一郎 岡
秀樹 鳥井
高田　泰廣
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2020561505A priority Critical patent/JP7176574B2/ja
Publication of WO2020130072A1 publication Critical patent/WO2020130072A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention provides a coating agent containing a silane condensate having a specific structure, and a coating film obtained by curing the coating agent. It also provides a laminate containing the coating film.
  • each of X 1 to X 3 independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula (2), and at least one of X 1 to X 3 is represented by the formula (2 ) Is a group represented by.
  • R 4 to R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • Z represents a bonding group having a urea or urethane bond
  • n3 represents a number of 1 to 3
  • l represents a number of 1 to 10
  • m represents a number of 1 to 10.
  • the coating agent of the present invention is a condensate having an isocyanuric ring structure and a (meth)acryloyl group, and is characterized by having a urea bond or a urethane bond in the condensate.
  • a urea bond or a urethane bond in the condensate, the wet heat resistance of the obtained coating film is improved.
  • the action of the urea bond or the urethane bond also improves the moldability and the resistance to cold and heat.
  • the urea bond and the urethane bond may have one or more of any one type in the condensate, and may have one or more of two types respectively.
  • R 4 to R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • Z represents a bonding group having a urea or urethane bond
  • n3 represents a number of 1 to 3
  • l represents a number of 1 to 10
  • m represents a number of 1 to 10.
  • R 4 to R 9 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom. .. Further, n3 is a number of 1 to 3, but is preferably 1. The above l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Further, m is a number of 1 to 10, preferably 1 to 8, and more preferably 1 to 6.
  • R 12 and R 13 represent an alkyl group having 1 to 15 carbon atoms or a hydrogen atom
  • R 14 represents a hydrogen atom or a methyl group
  • Y 4 represents an alkyl group having 1 to 10 carbon atoms, a urea bond and A bonding group having any one or a plurality of urethane bonds
  • n5 represents an integer of 1 to 3
  • n6 represents an integer of 1 to 3.
  • the compound having a structure having a urethane bond can be obtained by reacting a silane compound having an isocyanate group with a (meth)acrylate compound having a hydroxyl group. it can.
  • Examples of the (meth)acrylate compound having an isocyanate group include 2-isocyanate ethyl (meth)acrylate, 3-isocyanate propyl (meth)acrylate, 2-isocyanate propyl (meth)acrylate, 4-isocyanate butyl (meth)acrylate, 6 -Isocyanate hexyl (meth)acrylate, 8-isocyanate octyl (meth)acrylate, 10-isocyanate decane (meth)acrylate and the like.
  • R 15 to R 19 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • Z represents a bonding group having a urea or urethane bond
  • n7 represents a number of 1 to 3.
  • L represents a number from 1 to 10
  • m represents a number from 1 to 10.
  • the silane condensate of the present invention preferably has a structure (C) represented by the formula (5).
  • the structure (C) can be introduced by condensing the compound (A1) and the compound (B1), but preferably, alkoxysilane is blended and cocondensed.
  • composition of the present invention may contain other formulations.
  • Other compounds include various resins, reactive compounds, catalysts, polymerization initiators, organic fillers, inorganic fillers, organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, Flow control agent, coupling agent, dye, leveling agent, rheology control agent, UV absorber, antioxidant, plasticizer, etc., in addition to the silane condensate having the above structure, other silane condensate, for example, used for condensation And a single condensate or a complex condensate of the respective silane compounds.
  • the presence of water is required in the hydrolysis reaction.
  • the amount of water may be at least an amount sufficient to hydrolyze (a part of) the hydrolyzable groups in the silane compound or silicate compound, and may be 0 of the theoretical amount (mol) of the number of hydrolyzable groups. It is preferably an amount corresponding to 0.5 to 5.0 times mol.
  • the acidic catalyst is added as an aqueous solution, the water is included in the calculation. When the amount of water is small, sufficient hydrolysis does not proceed, and when the amount of water is large, the remaining water reduces the coatability and the drying efficiency.
  • ⁇ Dehydration condensation reaction of the silanol groups generated at the same time as hydrolysis occurs resulting in a siloxane resin.
  • the temperature at which this condensation is carried out is room temperature or under heating at 120° C. or lower, more preferably 30° C. or higher and 100° C. or lower. When the temperature is low, the hydrolysis and condensation reactions take a long time, resulting in low productivity, and when the temperature is higher than the range, insolubilization may occur.
  • the reactive compounds include monofunctional (meth)acrylate and polyfunctional (meth)acrylate.
  • Examples of the monofunctional (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (for example, trade name “Daicel Chemical Industries Ltd.” Praxel”), mono(meth)acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono(meth)acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono(meth)acrylate, polypropylene glycol Examples thereof include mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, and (meth)acrylic acid adducts of various epoxy esters.
  • a liquid organic polymer may be used to adjust the viscosity.
  • the liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha), Examples include amine salts of specially modified phosphoric acid esters (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymers (DISPERBYK2000; Big Chemie), and the like.
  • the resin composition of the present invention may contain a filler.
  • silica can be blended for the purpose of improving the hard coat property.
  • the silica is not limited, and known silica fine particles such as powdered silica and colloidal silica can be used.
  • commercially available powdery silica fine particles include, for example, Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd. E220A manufactured by Nippon Silica Industry Co., Ltd.
  • the blending amount of silica is preferably 3 to 60 parts by weight when the solid content of the total amount of the compound having (meth)acrylate and silica in the resin composition is 100 parts by weight.
  • the inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers, and other inorganic fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers). ), ceramics fibers, alumina fibers, natural fibers, mineral fibers such as basalt, boron fibers, boron nitride fibers, boron carbide fibers, and metal fibers.
  • the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless fibers, and steel fibers.
  • a polymerization initiator particularly a photopolymerization initiator.
  • Any known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used.
  • the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4 Examples include -(2-hydroxy-ethoxy)phenyl-(2-hydroxy-2-propyl)ketone.
  • Specific surface modifiers include EBECRYL350 (Daicel Ornex Co., Ltd.), BYK-333 (Big Chemie Japan Co., Ltd.), BYK-377 (Big Chemie Japan Co., Ltd.), BYK-378 (Big Chemie Japan Co., Ltd.).
  • BYK-UV3500 Big Chemie Japan Co., Ltd.
  • BYK-UV3505 Big Chemie Japan Co., Ltd.
  • BYK-UV3576 Big Chemie Japan Co., Ltd.
  • Megafac RS-75 (DIC Corporation), Megafac RS- 76-E (DIC Corporation), MegaFac RS-72-K (DIC Corporation), MegaFac RS-76-NS (DIC Corporation), MegaFac RS-90 (DIC Corporation), MegaFac RS- 91 (DIC Corporation), MegaFac RS-55 (DIC Corporation), Optool DAC-HP (Daikin Industry Co., Ltd.), ZX-058-A (T&K TOKA Corporation), ZX-201 (T&K TOKA Corporation) , ZX-202 (T&K TOKA Corporation), ZX-212 (T&K TOKA Corporation), ZX-214-A (T&K TOKA Corporation), X-22-164AS (Shin-Etsu Chemical Co., Ltd.), X
  • a coating film can be obtained by curing the coating agent of the present invention. Specifically, by coating the base material with the coating agent of the present invention and curing it, a laminate having a coating film can be obtained.
  • plastic substrate if necessary, within the range not impairing the effects of the present invention, if necessary, known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, light stabilizers, Known additives such as a crystal nucleating agent and a lubricant may be included.
  • Synthesis Example 8 Psi-2 UAS-03 133. Synthesized with 12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 9 g (0.29 mol), propylene glycol monomethyl ether (177.1 g), phosphoric acid: A-4 (0.19 g) and water (37.9 g) were added, and the mixture was heated to 80° C. and stirred for 4 hours. The solvent was removed to 80 wt%, and the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-2).
  • Synthesis Example 18 Psi-12 UAS-04 176. Synthesized with 12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 8 g (0.29 mol), 402.1 g of propylene glycol monomethyl ether, 0.19 g of phosphoric acid: A-4 and 37.9 g of water were added, the temperature was raised to 80° C. and the mixture was stirred for 4 hours. The solvent was removed to 80 wt%, and the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-12).
  • Ultraviolet irradiation uses a high pressure mercury lamp manufactured by GS-YUASA Co., Ltd., and the irradiation energy per pass is at a peak illuminance of 200 mW/cm 2 in the UV-A region of UV POWER PUCK II manufactured by EIT. 1000 mJ / cm 2 and so as lamp output, lamp height, and to adjust the conveyor speed, to the irradiation curing reaction in one pass (total 1000 mJ / cm 2), to obtain a laminate.

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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)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un agent de revêtement caractérisé en ce qu'il contient un condensat de silane qui a une structure (A) représentée par la formule (1), une structure (B) représentée par la formule (3), et une liaison uréthane et/ou une liaison urée.　La présente invention concerne également un film de revêtement obtenu par durcissement de l'agent de revêtement. La présente invention concerne également un stratifié ayant le film de revêtement.
PCT/JP2019/049800 2018-12-20 2019-12-19 Agent de revêtement, film de revêtement et stratifié WO2020130072A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020561505A JP7176574B2 (ja) 2018-12-20 2019-12-19 コーティング剤、コーティング膜及び積層体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018238333 2018-12-20
JP2018-238333 2018-12-20

Publications (1)

Publication Number Publication Date
WO2020130072A1 true WO2020130072A1 (fr) 2020-06-25

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PCT/JP2019/049800 WO2020130072A1 (fr) 2018-12-20 2019-12-19 Agent de revêtement, film de revêtement et stratifié

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JP (1) JP7176574B2 (fr)
WO (1) WO2020130072A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022203153A1 (fr) * 2021-03-26 2022-09-29 코오롱인더스트리 주식회사 Film optique ayant des propriétés de résistance au choc et de flexion excellentes et dispositif d'affichage le comprenant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011086958A1 (fr) * 2010-01-14 2011-07-21 関西ペイント株式会社 Composition durcissable par un rayonnement à énergie active et article revêtu
JP2013249395A (ja) * 2012-06-01 2013-12-12 Shin-Etsu Chemical Co Ltd 硬化性組成物及びその硬化成形品、その硬化皮膜が形成されてなる物品並びに該硬化性組成物の硬化方法
CN106569388A (zh) * 2015-09-30 2017-04-19 奇美实业股份有限公司 黑色矩阵用的感光性树脂组成物及其应用
JP2018083762A (ja) * 2016-11-21 2018-05-31 信越化学工業株式会社 有機ケイ素化合物を含む組成物並びにこれを含む塗料および接着剤

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003165955A (ja) * 2001-09-21 2003-06-10 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性樹脂組成物およびそれを塗布してなる塗装物。
JP5936448B2 (ja) * 2012-06-01 2016-06-22 関西ペイント株式会社 塗料組成物及び塗装物品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011086958A1 (fr) * 2010-01-14 2011-07-21 関西ペイント株式会社 Composition durcissable par un rayonnement à énergie active et article revêtu
JP2013249395A (ja) * 2012-06-01 2013-12-12 Shin-Etsu Chemical Co Ltd 硬化性組成物及びその硬化成形品、その硬化皮膜が形成されてなる物品並びに該硬化性組成物の硬化方法
CN106569388A (zh) * 2015-09-30 2017-04-19 奇美实业股份有限公司 黑色矩阵用的感光性树脂组成物及其应用
JP2018083762A (ja) * 2016-11-21 2018-05-31 信越化学工業株式会社 有機ケイ素化合物を含む組成物並びにこれを含む塗料および接着剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022203153A1 (fr) * 2021-03-26 2022-09-29 코오롱인더스트리 주식회사 Film optique ayant des propriétés de résistance au choc et de flexion excellentes et dispositif d'affichage le comprenant

Also Published As

Publication number Publication date
JP7176574B2 (ja) 2022-11-22
JPWO2020130072A1 (ja) 2021-11-18

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