WO2012111286A1 - Composition photopolymérisable, et élément entouré d'eau ainsi que panneau fonctionnel mettant en œuvre celle-ci - Google Patents

Composition photopolymérisable, et élément entouré d'eau ainsi que panneau fonctionnel mettant en œuvre celle-ci Download PDF

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WO2012111286A1
WO2012111286A1 PCT/JP2012/000882 JP2012000882W WO2012111286A1 WO 2012111286 A1 WO2012111286 A1 WO 2012111286A1 JP 2012000882 W JP2012000882 W JP 2012000882W WO 2012111286 A1 WO2012111286 A1 WO 2012111286A1
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photopolymerizable
meth
acrylate
photopolymerizable composition
general formula
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PCT/JP2012/000882
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English (en)
Japanese (ja)
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健延 石原
秀洋 赤間
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株式会社ブリヂストン
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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
    • 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
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the present invention relates to a photopolymerizable composition, and a water-surrounding member and a functional panel using the photopolymerizable composition, and in particular, easily drops water droplets attached to the surface of an article such as a water-surrounding member or a functional panel. It is possible and the effect relates to a photopolymerizable composition that is sustainable in the environment of use for a long time.
  • Functional panels as building materials are members that are arranged as the wall surface, floor surface, or ceiling wall surface of a building. Depending on the location, various functions such as soundproofing and humidity control are provided. Has been. Such a functional panel has various characteristics such as antifouling property, water resistance, moisture resistance, etc. that can withstand more severe use environment, especially when used as a water component in a bathroom, washroom or kitchen in a house. It is required to have. In particular, since the water circulating member is exposed to moisture or moisture, chemicals such as scales, molds, cleaning agents, and dyeing agents adhere to the members, and stains easily occur.
  • Patent Document 1 discloses a water-circulating member having a cured coating material containing a low surface free energy compound on its surface. Further, as the low surface free energy compound, a silicone resin compound and a fluororesin compound are used. It is disclosed.
  • Patent Document 2 discloses a resin molded body in which a low surface free energy layer is formed on the surface of the base resin, and the surface of the molded body is a surface having a low surface free energy compared to the surface of the base resin. Further, it is disclosed that the contact angle between the surface of the resin molded body and water is 90 degrees or more and 170 degrees or less, and the falling angle between the surface of the resin molded body and water is 1 degree or more and 80 degrees or less.
  • the low surface free energy surface produced using the low surface free energy compound repels water and forms spherical water droplets on the surface, the water droplets often adhere strongly to the surface and do not fall. It can be seen. Therefore, attempts have been made to drop the adhered water droplets from the surface by roughening the surface, etc., but the roughened surface has a problem in that it is easily durable and dirty. .
  • the present inventors can easily remove water droplets adhering to the surface of an article by using a silicon-containing compound having a specific structure as a constituent component of the photopolymerizable composition.
  • the present inventors have found that a photopolymerizable composition that can be dropped and can obtain a long-lasting effect in a use environment can be obtained, thereby completing the present invention.
  • the photopolymerizable composition of the present invention is (A) The following general formula (I): [Wherein R 2 is a hydrogen atom or a methyl group, n is an integer of 1 to 20, R 1 is an arbitrary organic group for introducing a (meth) acryloyl group into the side chain, and m is The number average molecular weight of the compound is a number arbitrarily selected within a range not departing from the range of 1000 to 40000], (B) a photopolymerizable oligomer and / or a photopolymerizable monomer polymerizable with the compound represented by the general formula (I), (C) A photopolymerization initiator is contained.
  • R 2 is a hydrogen atom or a methyl group
  • n is an integer of 1 to 20
  • R 1 is an arbitrary organic group for introducing a (meth) acryloyl group into the side chain
  • m is The number average molecular weight of the compound is a number arbitrarily selected
  • the photopolymerizable composition of the present invention preferably further contains (D) a fluorine-containing compound.
  • the mass ratio (A / D) of the compound (A) represented by the general formula (I) and the (D) fluorine-containing compound is preferably in the range of 0.2 to 10.0, 0.4 A range of ⁇ 5.0 is more preferred.
  • the content of the compound represented by (A) the general formula (I) is 100 parts by mass in total of the (B) photopolymerizable oligomer and photopolymerizable monomer.
  • the content of the fluorine-containing compound (D) is 0 to 5 parts by mass with respect to a total of 100 parts by mass of the (B) photopolymerizable oligomer and photopolymerizable monomer. 5 parts by mass.
  • the content of the compound represented by the general formula (I) is lower than 0.01 parts by mass, the ability to reduce the surface energy is not sufficiently exhibited, and when the content is more than 5 parts by mass, the photopolymerizable oligomer and the photopolymerizable are present. While compatibility with the monomer cannot be obtained and the effect of addition is saturated, the raw material cost of the photopolymerizable composition is increased.
  • the photopolymerizable oligomer is a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit.
  • the solubility parameter (SP value) of the photopolymerizable monomer is 20.0 (J / cm 3 ) 0.5 or less.
  • the water-surrounding member of the present invention is characterized by comprising a coating layer formed by curing the photopolymerizable composition and a base material layer.
  • the functional panel of the present invention is characterized by comprising a coating layer formed by curing the photopolymerizable composition and a base material layer.
  • the photopolymerizable composition of the present invention comprises (A) a compound represented by the above general formula (I), (B) a photopolymerizable oligomer and / or photopolymerizable with the compound represented by the general formula (I). It is characterized by containing a polymerizable monomer and (C) a photopolymerization initiator, and may contain other components as necessary.
  • (A) the compound represented by the general formula (I) is blended, and the compound is excellent not only in water repellency but also in water slidability. Therefore, articles coated with the photopolymerizable composition of the present invention, in particular, water-surrounding members and functional panels, have high water slidability of the coating layer, so that water droplets attached to the surface of the coating layer can be easily dropped. Can do.
  • the photopolymerizable composition of the present invention contains (A) a compound represented by the above general formula (I).
  • R 2 is a hydrogen atom or a methyl group
  • R 1 is an arbitrary organic group for introducing a (meth) acryloyl group into the side chain.
  • R 1 acts as a spacer for introducing a (meth) acryloyl group into the side chain, and depending on the type of organic group, silicone can be characterized.
  • an alkylene group as R 1 , lubricity and water repellency can be imparted to the photopolymerizable composition by the compound represented by the general formula (I). Thereby, a sufficient effect can be obtained even with a small addition amount.
  • the alkylene group may be linear or branched, and the length of the alkylene group is not particularly limited. However, in view of compatibility with the base resin, the alkylene group has 1 to 22 carbon atoms. It is preferable that it is the range of these.
  • R 1 is an ether group.
  • the compound of the formula (I) has a hydrophilic ether group, wide compatibility with the base resin can be ensured. Thus, an appropriate amount can be added to the system.
  • the ether group is represented by — (OR ′) q —, and R ′ is preferably a linear or branched alkylene group having 1 to 3 carbon atoms. These may be combined alone or in combination, and in the case of mixing, they may be block or random.
  • the repeat number q is an integer of 1 to 100.
  • n in the compound represented by the general formula (I) is an integer of 1 to 20.
  • a (meth) acryloyl group in the structure it reacts with (B) the photopolymerizable oligomer and / or photopolymerizable monomer that can be polymerized with the compound represented by the general formula (I) and is immobilized. Is done. Thereby, even if wiping or the like is repeated, the function can be maintained.
  • n exceeds 20
  • N is most preferably in the range of 2-6.
  • a preferred range of the weight average molecular weight of the compound represented by the general formula (I) is 1000 to 40000.
  • the weight average molecular weight can be determined from the retention time of a sample by preparing a calibration curve from a polystyrene standard by GPC. Tetrahydrofuran or chloroform can be used as the moving bed solvent for GPC. Moreover, a refractometer (RI), a UV detector, etc. can be used for a detector. When the weight average molecular weight obtained by using such a method is less than 1000, (A) the relative amount of dimethylsiloxane sites in the compound represented by the general formula (I) is decreased, so that a sufficient effect can be obtained.
  • the content of the compound represented by the general formula (I) is 100 parts by mass in total of (B) a photopolymerizable oligomer and a photopolymerizable monomer described later.
  • the range of 0.01 to 5 parts by mass is preferable, and the range of 0.1 to 3.0 parts by mass is more preferable.
  • the content of the compound represented by the general formula (I) is the amount of the active ingredient (solid content) of the compound represented by the general formula (I).
  • the content of the compound represented by the general formula (I) is 0.01 parts by mass or more, the water repellency and water slidability of the article coated with the photopolymerizable composition of the present invention can be sufficiently improved, Moreover, if it is 5 mass parts or less, (B) compatibility with a photopolymerizable oligomer and / or monomer is favorable, and a uniform hardened
  • the (B) photopolymerizable oligomer and / or photopolymerizable monomer used in the photopolymerizable composition of the present invention is a polymerizable unsaturated vinyl compound that can be polymerized with the compound represented by the general formula (I). And compounds having at least one (meth) acryloyl group [CH 2 ⁇ CHCO— or CH 2 ⁇ C (CH 3 ) CO—] capable of radical polymerization, unsaturated polyester resins, polybutadiene resins, and the like.
  • the compound represented by the above general formula (I) is excluded from the photopolymerizable oligomer and / or photopolymerizable monomer of the component (B).
  • the blending amount of the (B1) photopolymerizable oligomer and the (B2) photopolymerizable monomer is 100: 0 to 0: 100, preferably 80:20 to 20:80, more preferably 30: by mass ratio. It is in the range of 70 to 70:30. If the blending amount of the photopolymerizable monomer is too small, the viscosity of the resulting photopolymerizable composition may increase and the applicability may deteriorate, and physical properties such as chemical resistance and dye resistance cannot be secured sufficiently. there is a possibility. Moreover, when there are too many compounding quantities of a photopolymerizable monomer, the softness
  • the photopolymerizable oligomer is preferably a (meth) acrylate oligomer having one or more acryloyloxy groups [CH 2 ⁇ CHCOO—] or methacryloyloxy groups [CH 2 ⁇ C (CH 3 ) COO—],
  • a (meth) acrylate oligomer having a 2-polybutylene oxide unit is particularly preferred. Since the (meth) acrylate oligomer having the 1,2-polybutylene oxide unit has low polarity, it has good compatibility with the compound of the general formula (I), and the compound of the general formula (I) can be added over a wide range. Is possible.
  • the appearance after curing is good, and the water-surrounding members and functional panels using the same form a good appearance. be able to.
  • the resin obtained by curing the photopolymerizable composition has high hydrophobicity, it is highly resistant to water and stains such as detergents and hair colors used around the water, is not easily soiled, and is slippery. The long-term stability of is better.
  • (meth) acrylate oligomer examples include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, ether (meth) acrylate oligomers, ester (meth) acrylate oligomers, and polycarbonate (meth).
  • (Meth) acrylate oligomers such as acrylate oligomers and silicone-based (meth) acrylates may be mentioned.
  • (meth) acrylate oligomers include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolac type epoxy resin, adducts of polyhydric alcohol and ⁇ -caprolactone, (meth) It can be synthesized by reaction with acrylic acid or by urethanizing a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group.
  • the photopolymerizable oligomer may be a monofunctional oligomer, a bifunctional oligomer, or a polyfunctional oligomer, and is a polyfunctional oligomer from the viewpoint of realizing an appropriate crosslinking density of the resulting photopolymerizable composition. Is preferred.
  • urethane (meth) acrylate oligomers excellent in chemical resistance are preferable from the viewpoint of imparting suitable characteristics as a water surrounding member and a functional panel.
  • the urethane-based (meth) acrylate oligomer can be produced, for example, by synthesizing a urethane prepolymer from a polyol and a polyisocyanate, and adding a (meth) acrylate having a hydroxyl group to the urethane prepolymer.
  • the polyol used for the synthesis of the urethane prepolymer is a compound having a plurality of hydroxyl groups (—OH).
  • polyether polyol polyester polyol, polytetramethylene glycol, polybutadiene polyol, alkylene oxide-modified polybutadiene polyol and polyoxypolyol are used. Examples include isoprene polyol. These polyols may be used alone or in combination of two or more.
  • the polyether polyol can be obtained by addition polymerization.
  • an alkylene oxide such as ethylene oxide or propylene oxide is added to a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, or sorbitol.
  • polyether polyol can also be obtained by ring-opening polymerization, and examples of such polyether polyol include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF).
  • the polyester polyol can also be obtained by addition polymerization, for example, a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trimethylolethane, trimethylolpropane, It can be obtained from polyvalent carboxylic acids such as adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid and suberic acid.
  • a polyester polyol can also be obtained by ring-opening polymerization, and examples of such polyester polyol include lactone-based polyester polyols obtained by ring-opening polymerization of ⁇ -caprolactone.
  • the butylene oxide-modified polyol is a polyether polyol obtained by addition polymerization of 1,2-butylene oxide (BO) to a polyhydric alcohol in the presence of an alkali catalyst. Further, it may be a polyether polyol obtained by addition polymerization of not only 1,2-butylene oxide (BO) but also other alkylene oxides such as propylene oxide (PO). In this case, the ratio of BO to other alkylene oxide is 20:80 to 100: 0, preferably 50:50 to 100: 0, in terms of molar ratio.
  • the weight average molecular weight of these butylene oxide-modified polyols by GPC is usually 100 to 15,000, preferably 500 to 5,000.
  • the polyisocyanate is a compound having a plurality of isocyanate groups (—NCO).
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • CAde MDI crude diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • Examples include hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hexamethylene diisocyanate (HDI), isocyanurate-modified products, carbodiimide-modified products, and glycol-modified products.
  • HDI hexamethylene diisocyanate
  • isocyanurate-modified products carbodiimide-modified products
  • glycol-modified products glycol-modified products.
  • a catalyst for urethanization reaction is preferably used.
  • the catalyst for urethanization reaction include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide and the like; stannous chloride, etc.
  • Inorganic lead compounds organic lead compounds such as lead octenoate; cyclic amines such as triethylenediamine; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid; sulfuric acid, phosphoric acid, perchloric acid, etc.
  • Inorganic acids; bases such as sodium alcoholate, lithium hydroxide, aluminum alcoholate, sodium hydroxide; titanium compounds such as tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate; bismuth compounds; quaternary ammonium salts Etc.
  • organotin compounds are preferred. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably in the range of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of the polyol.
  • the (meth) acrylate having a hydroxyl group to be added to the urethane prepolymer has one or more hydroxyl groups, and is a (meth) acryloyloxy group [CH 2 ⁇ CHCOO— or CH 2 ⁇ C (CH 3 ) COO—]. Is a compound having one or more.
  • the (meth) acrylate having a hydroxyl group can be added to the isocyanate group of the urethane prepolymer. Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate. These (meth) acrylates having a hydroxyl group may be used alone or in combination of two or more.
  • the glass transition temperature exhibited by the coating layer obtained by curing the photopolymerizable composition can be optimized, and the effects excellent in water repellency, water slidability, etc.
  • a photopolymerizable composition that can be exhibited can be obtained.
  • Photopolymerizable Monomer a (meth) acrylate monomer having at least one acryloyloxy group [CH 2 ⁇ CHCOO—] or methacryloyloxy group [CH 2 ⁇ C (CH 3 ) COO—] is preferably used. Any of a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer can be used.
  • Monofunctional monomers include, for example, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , T-but
  • bifunctional monomer examples include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6.
  • polyfunctional monomer examples include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol.
  • examples include tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (meth) acrylate.
  • These (meth) acrylate monomers may be used alone or in combination of two or more.
  • the photopolymerizable monomer a photopolymerizable monomer having a solubility parameter (SP value) of 20.0 (J / cm 3 ) 0.5 or less is preferable.
  • the SP value can be estimated only from the chemical structure according to the Fedors method (see “Solubility Parameter Values”, Polymer Handbook, 4th edition (edited by J. Brandrup et al.)) .
  • the SP value means a value calculated by the Fedors method, and the lower the value, the lower the polarity of the photopolymerizable monomer (B).
  • the SP value of the photopolymerizable monomer is more preferably 19.6 (J / cm 3 ) 0.5 or less, and even more preferably 19.4 (J / cm 3 ) 0.5 or less.
  • the lower limit value of the SP value is not particularly limited, but usually 17.0 (J / cm 3 ) 0.5 or more is preferable.
  • (CH 2 CR 3 COO) p R 4 (II)
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is a p-valent hydrocarbon group having 5 to 20 carbon atoms, does not contain a hetero atom, and is cyclic even if it is a chain. May be.
  • —CH 2 — in the group may be replaced with —CH ⁇ CH—.
  • p is an integer of 1 to 4.
  • R 4 examples include —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH (CH 3 ) CH 3 , a cyclohexyl group, a cycloheptane group, a cyclooctane group, a cyclononane group, a cyclodecane group, and the like.
  • alkanetriyl groups such as those represented by C (CH 2 —) 4 .
  • the SP value of the monomer tends to increase in the case of a chain hydrocarbon group, and the acquisition itself becomes difficult in the case of a cyclic hydrocarbon group.
  • the number of carbon atoms in R 4 exceeds 20, in the case of a cyclic hydrocarbon group, the crosslinking density of the resulting photopolymerizable composition tends to decrease. If the crosslink density is lowered more than necessary, a dye such as a hair color tends to be leached into the coating layer, and the panel may be dyed.
  • the monomer represented by the formula (II) include isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, and isoamyl (meta).
  • 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, and dimethylol tricyclodecane di (meth) acrylate are preferable.
  • Nonanediol di (meth) acrylate and dimethyloltricyclodecane di (meth) acrylate are more preferable.
  • Such a monomer tends to exhibit good low polarity due to having a more suitable SP value, and not only the antifouling property of the water-surrounding member and functional panel obtained but also chemical resistance and dyeing resistance. It is possible to further improve the performance.
  • SP value solubility parameter
  • the compound of the general formula (I) can be added over a wide range. Therefore, even when the amount of the compound of the general formula (I) is large, white turbidity, layer separation, etc. can be suppressed, the appearance after curing is good, and the water-surrounding members and functional panels using the same form a good appearance. be able to.
  • the resin obtained by curing the photopolymerizable composition has high hydrophobicity, it is highly resistant to water and stains such as detergents and hair colors used around the water, is not easily soiled, and is slippery. The long-term stability of is better.
  • the number of functional groups of the photopolymerizable monomer is usually 1 to 6, preferably 1 to 4.
  • the number of functional groups is 1, the crosslinking density tends to increase.
  • the number of functional groups is 2 to 6, preferably 2 to 4, the crosslinking reaction of the photopolymerizable composition can be appropriately maintained. Therefore, it is presumed that the phenomenon in which the dyeing agent is leached into the coating layer and the water-surrounding member and the functional panel are dyed can be more effectively suppressed. Therefore, in this case as well, a water-surrounding member and a functional panel in which a coating layer having suitable curability is formed while effectively retaining not only good antifouling properties but also chemical resistance and dyeing resistance are provided. Obtainable.
  • the (C) photopolymerization initiator used in the photopolymerizable composition of the present invention is obtained by irradiating with light such as ultraviolet rays, whereby (A) the compound represented by the general formula (I) and (B) photopolymerization described above. It has the effect
  • Examples of the photopolymerization initiator (C) include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenylacetophenone, acetophenone diethyl ketal, alkoxyacetophenone, benzyldimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybenzophenone, benzophenone derivatives such as 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl, benzylmethyl ketal, etc.
  • Benzyl derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, Thiolene, thioxanthone and thioxanthone derivatives, fluorene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1 etc. are mentioned.
  • These photoinitiators (C) may be used individually by 1 type, and may be used in combination of
  • the blending amount of the (C) photopolymerization initiator in the photopolymerizable composition of the present invention is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the (B) photopolymerizable oligomer and photopolymerizable monomer. The range of is preferable.
  • the photopolymerizable composition of the present invention preferably further contains (D) a fluorine-containing compound.
  • (D) fluorine-containing compound By including the (D) fluorine-containing compound, the water repellency and water slidability of the photopolymerizable composition can be further improved.
  • any fluorine-containing compound can be used as the fluorine-containing compound.
  • (C) photopolymerization It is preferable that the fluorine-containing compound also has a photopolymerizable reactive group in the structure in the sense that it is immobilized in the system by reacting with a photopolymerizable composition containing an initiator.
  • a perfluoroalkyl group-containing photopolymerizable compound such as perfluorooctylethyl acrylate is exemplified.
  • the mass ratio (A / D) between the compound (A) represented by the general formula (I) and the (D) fluorine-containing compound is preferably in the range of 0.2 to 10.0, preferably 0.4 to 5. A range of 0 is more preferred.
  • the mass ratio (A / D) is the effective component ratio (solid content ratio) of the compound (A) represented by the general formula (I) and the (D) fluorine-containing compound in the photopolymerizable composition. .
  • both (D) the high water repellency derived from the fluorine-containing compound and the effect of both the water slidability derived from the compound represented by the above general formula (I)
  • concentration is 0.4 or more, the concentration of the fluorine-containing compound on the surface and the compound represented by the general formula (I) is increased. If it is 0 or less, (B) it is possible to achieve compatibility capable of copolymerization with a photopolymerizable oligomer and / or photopolymerizable monomer, and if it is 5.0 or less, better compatibility is achieved. It is possible to take
  • the content of the (D) fluorine-containing compound is in the range of 0 to 5 parts by mass with respect to a total of 100 parts by mass of the (B) photopolymerizable oligomer and photopolymerizable monomer.
  • the range of 0.1 to 3.0 parts by mass is more preferable.
  • the content of the fluorine-containing compound (D) is the amount (the amount of solid content) of the active ingredient of the fluorine-containing compound (D). (D) If the content of the fluorine-containing compound is 5 parts by mass or less, a sufficient improvement effect on water repellency and water slidability can be exhibited.
  • adding more than 5 parts by mass means from the viewpoint of characteristics and cost. If it is 3.0 parts by mass or less, a sufficient effect of improving water repellency / slidability without any practical problems can be expected. Moreover, if the content rate of (D) fluorine-containing compound is 0.1 mass part or more, the effect of improving the water repellency and water slidability of a photopolymerizable composition will become very large.
  • the photopolymerizable composition of the present invention may further contain a photosensitizer as necessary in consideration of the required curing reactivity and stability.
  • the photosensitizer absorbs energy when irradiated with light, and the energy or electrons move to the polymerization initiator to initiate polymerization.
  • Examples of the photosensitizer include p-dimethylaminobenzoic acid isoamyl ester.
  • the blending amount of these photosensitizers is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the photopolymerizable oligomer (B) and the photopolymerizable monomer.
  • the photopolymerizable composition of the present invention may contain a polymerization inhibitor as necessary in consideration of the required curing reactivity and stability.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol, butylhydroxyanisole, Examples include 3-hydroxythiophenol, ⁇ -nitroso- ⁇ -naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like.
  • the blending amount of these polymerization inhibitors is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the photopolymerizable oligomer (B) and the photopolymerizable monomer.
  • the photopolymerizable composition of the present invention may contain an organic solvent such as ether, ketone or ester as a diluting solvent.
  • organic solvent examples include propylene glycol monomethyl ether acetate (PMA), methyl ethyl ketone (MEK). ), Methyl isobutyl ketone (MIBK), acetone, or butyl lactate. These diluent solvents may be used alone or in combination of two or more.
  • the photopolymerizable composition of the present invention can be applied to the surface of the substrate as a coating liquid using a diluting solvent as necessary.
  • a known method can be adopted as a coating method, such as gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion. Examples thereof include a coat and a spin coat.
  • the water-surrounding member of the present invention comprises an application layer formed by curing the above-mentioned photopolymerizable composition and a base material layer.
  • the water-surrounding member of the present invention is a member that requires water drainage on the surface, for example, a kitchen sink, a wash basin, a bathroom wall material, a bathtub, a bathroom ceiling material, a bathroom floor material, a bathroom counter, and a toilet And water storage tanks.
  • the functional panel of the present invention comprises an application layer formed by curing the above-mentioned photopolymerizable composition and a base material layer.
  • the application layer is formed on the base material layer. It is preferable.
  • the thickness of the entire functional panel of the present invention is preferably 2.5 mm or more.
  • the upper limit of the thickness of the entire functional panel is not particularly limited, and the coating layer may be formed on both the front surface and the back surface of the base material layer.
  • a multilayer structure in which an intermediate layer made of various materials is formed between these layers may be used.
  • the coating layer has excellent water repellency and water slidability as described above, it is desirable to form the coating layer as the outermost surface layer of the functional panel.
  • middle layer the undercoat layer for improving the adhesiveness of a base material layer and a coating layer, the decorative layer which provided the pattern and color for improving the designability of a functional panel, etc. are mentioned, for example.
  • the water-surrounding member and functional panel of the present invention thus obtained have excellent water repellency and water slidability as well as warm water resistance and dye resistance because the coating layer is formed on the base material layer. It is also excellent in properties, and it is difficult to cause alteration or deterioration even by using a highly irritating cleaning agent containing acid or alkali while effectively suppressing the adhesion of various types of dirt typified by scale. Further, discoloration and dyeing hardly occur even when a dyeing agent such as a hair color is used. Therefore, the water-surrounding member and the functional panel of the present invention are particularly suitable as a functional panel disposed in a bathroom or kitchen in a house.
  • An application layer can be formed on a base material layer by applying the photopolymerizable composition onto a base material, followed by photocuring.
  • a method of photocuring a method of irradiating light such as ultraviolet rays is common.
  • the surface on the base material layer forming the coating layer may be only one surface or both surfaces of the front surface and the back surface, and may be appropriately selected as necessary.
  • the irradiation amount of light for curing the photopolymerizable composition when employing ultraviolet light, usually, the irradiation intensity 20 ⁇ 2000mW / cm 2, an irradiation amount 100 ⁇ 5000mJ / cm 2, whereby the light
  • the polymerizable composition is usually cured in several seconds to several tens of seconds.
  • the thickness of the coating layer can be appropriately selected from the required degree of designability and chemical resistance, and is not particularly limited, but is normally assumed to be in the range of 1 ⁇ m to 200 ⁇ m.
  • the ultraviolet curing reaction is a radical reaction, it is susceptible to inhibition by oxygen. Therefore, after applying the photopolymerizable composition to a substrate, the composition may be cured under a nitrogen atmosphere so that contact with oxygen can be avoided.
  • the surface free energy of the coating layer formed by photocuring is usually preferably 12 to 30 mJ / m 2 from the viewpoint of sufficiently ensuring good water repellency and water slidability.
  • the coating layer preferably has a falling angle of 30 ⁇ L of water droplets of 40 ° or less, and more preferably 20 ° or less. If the falling angle of 30 ⁇ L of water droplets on the coating layer is 40 ° or less, water easily slides down from the water surrounding member and the functional panel.
  • the mass ratio (A / D) of the compound (A) represented by the general formula (I) and the (D) fluorine-containing compound is 0.2. It is preferable to set it to ⁇ 10.0.
  • the mass ratio (A / D) of the compound (A) represented by the general formula (I) and the (D) fluorine-containing compound is set to 0.4 to Preferably it is 5.0.
  • Base material layer As a material of the base material layer used for the water-surrounding member and the functional panel of the present invention, inorganic materials such as slate, concrete, metal, calcium silicate, calcium carbonate, and glass; wooden material, polypropylene, polystyrene, polycarbonate, Organic materials such as unsaturated polyester resins; and composite materials thereof. Among these, a material obtained by adding fibers such as glass fiber and carbon fiber to an organic material, so-called FRP (fiber reinforced plastic) is preferable. Examples of the FRP include an unsaturated polyester resin, a sheet-like sheet molding compound (SMC) containing a filler and glass fiber or carbon fiber, and a BMC having a composite material similar to SMC and containing short fibers.
  • SMC sheet-like sheet molding compound
  • FRP is a blend of a thermosetting resin, an organic peroxide (curing agent), a filler, a low shrinkage agent, an internal mold release agent, a reinforcing material, a crosslinking agent, a thickener, and the like. It is used by being put in a mold set at a predetermined temperature and pressurized, and shaped into a shape according to the place to be arranged as a building material.
  • the FRP contains unsaturated polyester as a thermosetting resin, a filler, and glass fiber or carbon fiber as a reinforcing material, the strength and durability of the water-surrounding member and the functional panel as a whole are further improved. be able to.
  • Unsaturated polyesters include polybasic unsaturated acids such as maleic anhydride and fumaric acid, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, trimethylpentanediol, neopentyl glycol, trimethylpropane monoallyl. It is produced from polyhydric alcohols such as ether, hydrogenated bisphenol and bisphenol dioxypropyl ether.
  • fillers examples include calcium carbonate and aluminum hydroxide.
  • Calcium carbonate is preferable from the viewpoint of cost reduction
  • aluminum hydroxide is preferable from the viewpoint of improving the chemical resistance of FRP itself.
  • the coating layer is formed, the chemical resistance of the water-surrounding member and the entire functional panel can be sufficiently improved even if FRP using calcium carbonate as a base material is used. Therefore, a water-surrounding member and a functional panel having a base layer made of low-cost FRP can be easily realized.
  • Glass fibers and carbon fibers as reinforcing materials having a fiber length of about 20 to 50 mm and a fiber diameter of about 5 to 25 ⁇ m are preferably used, and are contained in FRP in an amount of 10 to 70% by mass. Is desirable.
  • the FRP used as the substrate layer is manufactured as an FRP having a predetermined thickness and size by mixing these components and using an FRP manufacturing apparatus or the like.
  • the thickness of a base material layer may be fluctuate
  • the upper limit of the thickness is not particularly limited and can be appropriately selected.
  • each component was charged and mixed in a stirrer to prepare a photopolymerizable composition.
  • the obtained photopolymerizable composition was applied so as to have a thickness of 20 ⁇ m with respect to the upper surface of a substrate made of FRP (Deckmat (registered trademark) 2415, manufactured by DIC Kako Co., Ltd.).
  • UV irradiation 500 mW / cm 2 , 300 mJ / cm 2
  • an evaluation sample was prepared.
  • the dyeing property with respect to the hair color was evaluated by the following method in order to confirm the falling angle and the stain resistance in the use environment, and the results shown in Tables 1 to 3 were obtained.
  • the falling angles of PET films and FRP (fiber reinforced plastic) plates were evaluated, and the results shown in Table 4 were obtained.
  • Rolling angle DM-500 and DM-SA manufactured by Kyowa Interface Science Co., Ltd. were used for measuring the rolling angle. 30 ⁇ l of water droplets were dropped on the substrate, the stage was tilted at a speed of 7.5 degrees / second, and the angle at which the water droplets started to move was defined as the contact angle value. The measurement was performed twice, and the average value was taken as the value of the sliding angle.
  • Polyol was obtained by adding 12 mol of butylene oxide to 1 mol of propylene glycol (Kanto Chemical Co., Ltd.) using potassium hydroxide as a catalyst at a reaction temperature of 110 ° C. To the polyol, 2 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
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Abstract

L'invention concerne une composition de résine photodurcissable permettant de faire tomber facilement des gouttes d'eau qui adhèrent à la surface d'un article. Plus précisément, l'invention concerne une composition de résine photodurcissable qui est caractéristique en ce qu'elle comprend : (A) un composé représenté par la formule générale (I) (Dans la formule : R2 représente un atome d'hydrogène ou un groupe méthyle; n représente un entier de 1 à 20; R1 représente un groupe organique arbitraire destiné à introduire un groupe (méth)acryloyle dans une chaîne latérale; et m représente un nombre choisi arbitrairement dans une plage ne s'éloignant pas d'une plage telle que la masse moléculaire moyenne en poids du composé est de 1000 à 40000); (B) un oligomère photopolymérisable et/ou un monomère photopolymérisable polymérisables avec le composé représenté par ladite formule générale (I); et (C) un initiateur de photopolymérisation.
PCT/JP2012/000882 2011-02-14 2012-02-09 Composition photopolymérisable, et élément entouré d'eau ainsi que panneau fonctionnel mettant en œuvre celle-ci WO2012111286A1 (fr)

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EP3604393A4 (fr) * 2017-03-29 2020-12-30 Shin-Etsu Chemical Co., Ltd. Composé siloxane modifié par un (méth)acrylique
EP3604394A4 (fr) * 2017-03-29 2020-12-30 Shin-Etsu Chemical Co., Ltd. Macromonomère de silicone modifié par un (méth)acrylique

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KR101806746B1 (ko) 2016-11-09 2017-12-08 황진상 디스플레이 접착제용 불소화 수지 조성물의 제조방법 및 이를 이용한 불소화 수지 조성물
TWI756399B (zh) * 2017-03-29 2022-03-01 日商三菱化學股份有限公司 (甲基)丙烯酸系共聚合物、其製造方法、樹脂組成物及防污塗料組成物
JP2019131682A (ja) * 2018-01-31 2019-08-08 三菱ケミカル株式会社 硬化性重合体組成物及び積層体
JP7207281B2 (ja) * 2019-12-02 2023-01-18 信越化学工業株式会社 紫外線硬化型シリコーン組成物およびその硬化物

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