WO2016190373A1 - Composition de résine durcissable, et procédé de fabrication ce celle-ci - Google Patents

Composition de résine durcissable, et procédé de fabrication ce celle-ci Download PDF

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Publication number
WO2016190373A1
WO2016190373A1 PCT/JP2016/065513 JP2016065513W WO2016190373A1 WO 2016190373 A1 WO2016190373 A1 WO 2016190373A1 JP 2016065513 W JP2016065513 W JP 2016065513W WO 2016190373 A1 WO2016190373 A1 WO 2016190373A1
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Prior art keywords
resin composition
curable resin
meth
acrylate
inorganic oxide
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PCT/JP2016/065513
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English (en)
Japanese (ja)
Inventor
吉田　和徳
雄太 村上
佳一郎 井上
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三洋化成工業株式会社
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Priority to KR1020177030840A priority Critical patent/KR20170129944A/ko
Priority to JP2017520792A priority patent/JP6826528B2/ja
Publication of WO2016190373A1 publication Critical patent/WO2016190373A1/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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a curable resin composition and a method for producing the same. Specifically, the present invention relates to a curable resin composition that provides a cured product having excellent transparency and high hardness, and a method for producing the same.
  • display devices such as a liquid crystal display and a touch panel display provided with a film having a hard coat film as a protective layer on the surface are rapidly spreading.
  • electronic devices such as smartphones and tablet terminals equipped with a touch panel that is operated by directly touching the screen with a finger or a pen are remarkably widespread, and such devices are required to improve the hardness of the touch panel surface.
  • a resin such as PET or acrylic that is safer and lighter than glass.
  • these resins have a drawback in that they are inferior in hardness to glass.
  • the ultraviolet curable resin composition produced by this method has a problem that the content of silica particles is limited from the viewpoint of the transparency of the cured product, and the desired film hardness cannot be obtained.
  • JP 2000-264621 A JP2015-86103A Japanese Patent Laid-Open No. 2015-36402
  • An object of the present invention is to provide a curable resin composition capable of providing a cured product having excellent transparency and high hardness, and a method for producing the same.
  • the present invention contains an inorganic oxide (A) and a polyfunctional (meth) acrylate (B), the content of the inorganic oxide (A) is 25 to 80% by weight, and the curable resin composition Curable resin composition (C), wherein the total light transmittance is 90% or more and satisfies the following relational expression (1); and inorganic oxide (A) and polyfunctional (meth) acrylate (B) is a method for producing a curable resin composition (C), which comprises an inorganic alkoxide (a1), a metal inorganic, in a polyfunctional (meth) acrylate (B) in the presence of a catalyst (b).
  • the curable resin composition of the present invention has an effect that it can provide a cured product having excellent transparency and high hardness. Even if the curable resin composition of the present invention contains a large amount of fine particles of inorganic oxide such as silica, the transparency is not impaired and a cured product having high hardness can be obtained. According to the method for producing a curable resin composition of the present invention, it is possible to produce a curable resin composition that can provide a cured product having excellent transparency and high hardness.
  • the curable resin composition (C) of the present invention contains an inorganic oxide (A) and a polyfunctional (meth) acrylate (B), and the content of the inorganic oxide (A) is 25 to 80% by weight. And the total light transmittance of the curable resin composition is 90% or more.
  • the curable resin composition (C) of the present invention further satisfies the following relational expression (1). T ⁇ 91-1.25 ⁇ W / 100 (1) [Wherein, W represents the content (% by weight) of the inorganic oxide (A) in the curable resin composition, and T represents the total light transmittance (%) of the curable resin composition. ]
  • examples of the inorganic oxide (A) include inorganic oxides such as silica, zirconium, titanium, hafnium, zinc, aluminum, gallium, indium, germanium, and tin. 1 type may be sufficient as an inorganic oxide (A), and 2 or more types may be sufficient as it.
  • the content of the inorganic oxide (A) in the curable resin composition (C) of the present invention is 25 to 80% by weight, preferably 30 to 70% by weight. More preferably 30 to 60% by weight.
  • the hardness of the cured product is insufficient, and when it exceeds 80% by weight, the transparency of the cured product is deteriorated.
  • the said content is defined as those totals.
  • the inorganic oxide (A) preferably has a hydroxyl group, and the inorganic oxide (A) is selected from the group consisting of an inorganic alkoxide (a1), a metal inorganic acid salt (a2) and an inorganic chloride (a3). It is preferable that it is a hydrolysis-condensation product of the inorganic oxide precursor (a) of a kind or more, and as such a hydrolysis-condensation product, in the polyfunctional (meth) acrylate (B), in the presence of the catalyst (b). Obtained by reacting water with at least one inorganic oxide precursor (a) selected from the group consisting of inorganic alkoxide (a1), metal inorganic acid salt (a2) and inorganic chloride (a3) Is more preferable.
  • the polyfunctional (meth) acrylate (B) contained in the curable resin composition (C) of the present invention has at least 2, preferably 3-6 (meth) acryloyl groups from the viewpoint of the hardness of the cured product.
  • Polyfunctional (meth) acrylates having the following are preferred.
  • the polyfunctional (meth) acrylate (B) the following di (meth) acrylate (B1), trivalent or higher (meth) acrylate (B2), polyester (meth) acrylate (B3), urethane ( Examples include (meth) acrylate (B4), epoxy (meth) acrylate (B5), (meth) acryloyl group-modified butadiene polymer (B6), and (meth) acryloyl group-modified dimethylpolysiloxane polymer (B7).
  • di (meth) acrylate (B1) polyoxyalkylene (alkylene having 2 to 4 carbon atoms) [number average molecular weight 106 to 3,000 (hereinafter, the number average molecular weight is determined by gel permeation chromatography (GPC)). )] Means a number average molecular weight by the method, abbreviated as Mn.)] Di (meth) acrylate (B11): polyethylene glycol (preferably Mn 100 to 800, more preferably Mn 300 to 500), polypropylene glycol (preferably Mn 100 To 500, more preferably Mn 150 to 300) and polytetramethylene glycol (preferably Mn 400 to 1000, more preferably Mn 500 to 800).
  • the di (meth) acrylate (B1) is an alkylene oxide of a dihydric phenol compound (hereinafter, “alkylene oxide” is abbreviated as AO) (2 to 30 mol) of an adduct di (meth) acrylate: 2 Of polyhydric phenol compounds [monocyclic phenols (catechol, resorcinol, hydroquinone, etc.), condensed polycyclic phenols (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, -F, -S, etc.)] [resorcinol ethylene oxide ( EO) 4 mol adduct di (meth) acrylate, dihydroxynaphthalene propylene oxide (PO) 4 mol adduct di (meth) acrylate, bisphenol A, -F or -S, EO 2 mol, or PO 4 mol each addition Di (meth) acrylate of Door and the like.
  • AO alkylene oxide
  • di (meth) acrylate (B1) examples include di (meth) acrylates of aliphatic dihydric alcohols having 2 to 30 carbon atoms: each di (meth) acrylate of neopentyl glycol and 1,6-hexanediol.
  • Di (meth) acrylate (B1) di (meth) acrylate of dihydric alcohol containing 6-30 carbon atoms: di (meth) acrylate of dimethyloltricyclodecane, di (meth) acrylate of cyclohexanedimethanol And di (meth) acrylate of hydrogenated bisphenol A.
  • di (meth) acrylate (B1) hydroxyl groups such as di (meth) acrylate of polyhydric alcohol having 3 to 40 carbon atoms: trimethylolpropane EO 3 mol adduct di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.
  • numerator is also mentioned.
  • Examples of the trivalent or higher (meth) acrylate (B2) include polyhydric alcohols having 3 to 40 carbon atoms and poly (meth) acrylates of AO adducts thereof: Trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane EO3 mol or PO3 mol adduct tri (meth) acrylate, glycerol EO3 mol or PO3 mol adduct tri (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol EO 4 mol adduct tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaery
  • the polyfunctional (meth) acrylate (B) preferably has a reactive group ( ⁇ ) that reacts with a hydroxyl group in the inorganic oxide (A) to form a chemical bond.
  • the trivalent or higher (meth) acrylate (B21) having a hydroxyl group as the reactive group ( ⁇ ) in the molecule is an ester reaction product of a polyhydric alcohol and acrylic acid or methacrylic acid. Having at least one of the above.
  • Examples of the trivalent or higher (meth) acrylate (B21) having a hydroxyl group in the molecule include, for example, pentaerythritol tri (meth) acrylate; pentaerythritol EO adduct tri (meth) acrylate; dipentaerythritol Penta (meth) acrylate, tetra (meth) acrylate of dipentaerythritol, tri (meth) acrylate of dipentaerythritol, penta (meth) acrylate of EO adduct of dipentaerythritol; poly (meth) acrylate of tripentaerythritol Etc.
  • ester reactions of polyhydric alcohols with acrylic acid or methacrylic acid are generally not chemically equivalent and are polyfunctional (meth) acrylates having different numbers of ester bonds (ie, the number of hydroxyl groups) ( A mixture of B) is obtained.
  • a mixture of B is obtained.
  • the pentaacrylate or hydroxyl group of dipentaerythritol having 1 hydroxyl group is usually used.
  • Two dipentaerythritol tetraacrylates are also by-produced and become a mixture thereof.
  • Such a mixture can also be used as the polyfunctional (meth) acrylate (B) of the present invention.
  • the polyester (meth) acrylate (B3) includes a plurality of ester bonds and five or more (meth) acryloyl groups obtained by esterification of a polycarboxylic acid, a polyhydric alcohol, and an ester-forming (meth) acryloyl group-containing compound. Examples thereof include polyester (meth) acrylates having a Mn of 150 or more and a Mn of 4,000 or less.
  • polyvalent carboxylic acid examples include aliphatic polycarboxylic acids [for example, malonic acid, maleic acid (anhydride), adipic acid, sebacic acid, succinic acid, acid anhydride reaction products (dipentaerythritol and maleic anhydride). Acid reactants)], cycloaliphatic polycarboxylic acids [eg cyclohexanedicarboxylic acid, tetrahydro (anhydride) phthalic acid, methyltetrahydro (anhydride) phthalic acid] and aromatic polycarboxylic acids [eg isophthalic acid, terephthalic acid Phthalic acid (anhydride)].
  • aliphatic polycarboxylic acids for example, malonic acid, maleic acid (anhydride), adipic acid, sebacic acid, succinic acid, acid anhydride reaction products (dipentaerythritol and maleic anhydride). Acid reactants)]
  • Examples of the polyhydric alcohol include ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol and the like.
  • Examples of the ester-forming (meth) acryloyl group-containing compound include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and the like.
  • urethane (meth) acrylate (B4) Mn400 or more having a plurality of urethane bonds and two or more (meth) acryloyl groups obtained by urethanization reaction of polyisocyanate, polyol, and hydroxyl group-containing (meth) acrylate
  • urethane (meth) acrylate having Mn of 5,000 or less can be mentioned.
  • polyisocyanate examples include aliphatic polyisocyanate [hexamethylene diisocyanate and the like], aromatic (aliphatic) polyisocyanate [2,4- or 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, and the like. And cycloaliphatic polyisocyanates [isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and the like].
  • polyol examples include ethylene glycol, 1,4-butanediol, neopentyl glycol, polyether polyol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, and polytetramethylene glycol.
  • hydroxyl group-containing (meth) acrylate examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
  • Examples of the epoxy (meth) acrylate (B5) include an epoxy (meth) acrylate having a Mn of 400 or more and a Mn of 5,000 or less obtained by a reaction between a polyvalent (2 to 4 valent) epoxide and (meth) acrylic acid.
  • Examples of the (meth) acryloyl group-modified butadiene polymer (B6) include polybutadiene poly (meth) acrylate (Mn 500 to 500,000) having a (meth) acryloyl group in the main chain and / or side chain.
  • (Meth) acryloyl group-modified dimethylpolysiloxane polymer (B7) includes dimethylpolysiloxane poly (meth) acrylate having Mn of 300 to 20,000 having (meth) acryloyl group in the main chain and / or side chain.
  • the above (B1) to (B7) may be used alone or in combination of two or more.
  • (B1) to (B7) from the viewpoint of the hardness of the cured product, (B2) to (B7) are preferable, and (B2) and (B4) are more preferable.
  • monofunctional (meth) acrylate may be used in combination.
  • the polyfunctional (meth) acrylate (B) in the present invention more preferably contains a polyfunctional (meth) acrylate (B) having a reactive group ( ⁇ ) capable of reacting with a hydroxyl group.
  • the content of the polyfunctional (meth) acrylate having a reactive group ( ⁇ ) in the polyfunctional (meth) acrylate (B) is preferably 50 mol% or more, more preferably 90 mol% or more.
  • the polyfunctional (meth) acrylate (B) is more preferably a polyfunctional (meth) acrylate (B) having a reactive group ( ⁇ ).
  • Examples of the reactive group ( ⁇ ) capable of reacting with a hydroxyl group include a hydroxyl group, a carboxyl group, an amino group, a thiol group, a sulfonic acid group, a phosphoric acid group, and an amide group.
  • the reactive group ( ⁇ ) reacts with the hydroxyl group in the inorganic oxide (A), and a chemical bond is generated at the organic-inorganic interface, so that high hardness is exhibited.
  • a hydroxyl group, a carboxyl group, and a phosphate group are preferred, a hydroxyl group or a carboxyl group is more preferred, and a hydroxyl group is most preferred.
  • the polyfunctional (meth) acrylate (B) contains a polyfunctional (meth) acrylate having a reactive group ( ⁇ ) capable of reacting with a hydroxyl group, and is an inorganic oxide.
  • (A) has a hydroxyl group, and at least a part of the reactive group ( ⁇ ) in the polyfunctional (meth) acrylate (B) reacts with at least a part of the hydroxyl group in the inorganic oxide (A) to react with the chemistry. Bonding is preferred.
  • the content of the polyfunctional (meth) acrylate (B) is hardness and transparency. In view of the above, it is usually 20 to 75% by weight, preferably 25 to 70% by weight, and more preferably 30 to 60% by weight.
  • the said content is defined as those totals.
  • the total light transmittance of the curable resin composition (C) of the present invention is 90% or more.
  • the total light transmittance in the present invention is determined in accordance with JIS-K7105 by sandwiching the curable resin composition between two slides as described in detail in the measurement method of the examples. Measure with JIS-K7105
  • An object of the present invention is to provide a curable resin composition that is excellent in transparency and can provide a cured product having high hardness.
  • the content of the inorganic oxide (A) Increasing the value has a contradictory relationship of impairing transparency. Therefore, the curable resin composition (C) of the present invention satisfies the following relational expression (1) regarding the content of the inorganic oxide (A) and the total light transmittance of the curable resin composition.
  • W represents the content (% by weight) of the inorganic oxide (A) in the curable resin composition
  • T represents the total light transmittance (%) of the curable resin composition.
  • fine particles of general inorganic oxide for example, silica fine particles are mixed with the polyfunctional (meth) acrylate (B).
  • the content of the silica fine particles is to be increased more than 25% by weight, the transparency tends to be impaired.
  • the curable resin composition (C) of the present invention in the polyfunctional (meth) acrylate (B), in the presence of the catalyst (b), the inorganic alkoxide (a1), the metal inorganic acid salt ( It is preferable to include a step of obtaining inorganic oxide (A) by reacting one or more inorganic oxide precursors (a) selected from the group consisting of a2) and inorganic chloride (a3) with water.
  • the inorganic oxide (A) contained in the curable resin composition (C) of the present invention thus reacts the inorganic oxide precursor (a) with water in the polyfunctional (meth) acrylate (B).
  • the inorganic oxide (A) is excellent in compatibility with the polyfunctional (meth) acrylate (B).
  • the curable resin composition contains the inorganic oxide (A) thus obtained, the hardness of the cured product is increased.
  • the inorganic oxide (A) is obtained by the above method, the cured product can be obtained even if the content of the inorganic oxide (A) in the curable resin composition (C) is 25 to 80% by weight. Is excellent in transparency.
  • the curable resin composition (C) of the present invention is not produced by mixing the inorganic oxide (A) with the polyfunctional (meth) acrylate (B), but the inorganic oxide precursor (a) and water.
  • the hydrolysis condensate of the inorganic oxide precursor (a) produced by reacting in the polyfunctional (meth) acrylate (B) in the presence of the catalyst (b) is preferably used as the inorganic oxide (A).
  • the inorganic oxide (A) is a hydrolyzate of one or more inorganic oxide precursors (a) selected from the group consisting of inorganic alkoxides (a1), metal inorganic acid salts (a2) and inorganic chlorides (a3).
  • a decomposition condensate is preferred.
  • the inorganic oxide (A) which is a hydrolysis-condensation product of the inorganic oxide precursor (a) is preferable because it usually has a hydroxyl group.
  • Examples of the inorganic alkoxide (a1) include silicon alkoxide, zirconium alkoxide, titanium alkoxide, hafnium alkoxide, zinc alkoxide, aluminum alkoxide, gallium alkoxide, indium alkoxide, germanium alkoxide, and tin alkoxide. These may be used alone or in combination of two or more. Among these, silica alkoxide, titanium alkoxide, and zirconium alkoxide are preferable from the viewpoint of hardness.
  • the silica alkoxide is preferably tetraethoxysilane or tetra-n-butoxysilane, and the titanium alkoxide is preferably tetraethoxytitanium or tetra-n-butoxytitanium.
  • Examples of the metal inorganic acid salt (a2) include a combination of a metal such as titanium or zirconium and an inorganic acid such as nitric acid or sulfuric acid.
  • a metal such as titanium or zirconium
  • an inorganic acid such as nitric acid or sulfuric acid.
  • Specific examples include titanium nitrate, titanium oxysulfate, zirconium oxynitrate, and zirconium sulfate. Etc. These may be used alone or in combination of two or more. Of these, titanium tetranitrate, titanium oxysulfate, and zirconium oxynitrate are preferable. These may be used alone or in combination of two or more.
  • Examples of the inorganic chloride (a3) include metal chlorides and nonmetal chlorides, such as titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, zinc chloride, aluminum chloride, gallium chloride, indium chloride, tin chloride, and the like. And metal chlorides such as silicon tetrachloride and germanium tetrachloride. These may be used alone or in combination of two or more. Among these, preferred are chlorides such as silicon, titanium and zirconium, specifically silicon tetrachloride, titanium tetrachloride and zirconium tetrachloride.
  • inorganic alkoxides (a1) are preferred.
  • the polyfunctional (meth) acrylate (B) used for production of the inorganic oxide (A) is the same as the polyfunctional (meth) acrylate (B) described above.
  • the polyfunctional (meth) acrylate (B) preferably contains a polyfunctional (meth) acrylate having a reactive group ( ⁇ ) that can react with a hydroxyl group, and has a reactive group ( ⁇ ) that can react with a hydroxyl group. More preferably, it is a functional (meth) acrylate.
  • the inorganic alkoxide (a1), the metal inorganic acid salt (a2) and the inorganic chloride (a3) are formed in the presence of the catalyst (b).
  • the catalyst (b) By reacting one or more inorganic oxide precursors (a) selected from the group with water, the inorganic oxide (A) and the polyfunctional (meth) acrylate (B) are contained, and the polyfunctional (meta ) Producing a curable resin composition in which at least a part of the reactive group ( ⁇ ) in the acrylate (B) and at least a part of the hydroxyl group in the inorganic oxide (A) are reacted and chemically bonded. Can do.
  • Such a curable resin composition is preferable as the curable resin composition (C) of the present invention.
  • the usage-amount of polyfunctional (meth) acrylate (B) in manufacture of an inorganic oxide (A) is not specifically limited,
  • the total weight of an inorganic oxide precursor (a) and a polyfunctional (meth) acrylate (B) is preferably 20 to 75% by weight, more preferably 25 to 70% by weight, still more preferably 30 to 60% by weight.
  • the inorganic oxide precursor (a) and water are preferably reacted in the presence of the catalyst (b), and examples of the catalyst (b) include an acid catalyst (b1) and a base catalyst (b2). Of these, the acid catalyst (b1) is preferred.
  • the amount of the catalyst (b) used may be appropriately selected depending on the type of the catalyst and the like. For example, it is preferable to use 0.1 to 15 parts by weight with respect to 100 parts by weight of the inorganic oxide precursor (a). It is more preferable to use 1 to 10 parts by weight.
  • Examples of the acid catalyst (b1) include inorganic acids and organic acids.
  • Examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid.
  • Examples of the organic acid include sulfonic acid (such as p-toluenesulfonic acid), carboxylic acid, hydroxy acid, and oxalic acid.
  • Examples of the base catalyst (b2) include metal hydroxides and organic amines, and examples of the metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide.
  • organic amines include aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines.
  • aliphatic amine include mono- having 1 to 18 carbon atoms in the alkyl group such as hexylamine, octylamine, methylhexylamine, methyloctylamine, dimethylhexylamine, dimethyloctylamine, dimethyllaurylamine, and dimethylcetylamine, Di- or tri-alkylamines are mentioned.
  • alicyclic amine examples include cycloalkylamine having 4 to 12 carbon atoms in the cycloalkyl group such as cyclobutylamine, cyclohexylamine, cyclopentylamine, cyclooctylamine, N-methylcyclohexylamine, and N-ethylcyclohexylamine, and the like.
  • Examples include alkyl (having 1 to 6 carbon atoms) substituents.
  • aromatic amine examples include aromatic amines having 6 to 18 carbon atoms such as aniline and diphenylamine.
  • heterocyclic amine examples include heterocyclic amines having 4 to 10 carbon atoms such as morpholine.
  • Molar ratio of inorganic oxide precursor (a) to water (inorganic oxide precursor (a) / water) when forming a hydrolyzed condensate of inorganic oxide precursor (a) as inorganic oxide (A) ) Is preferably 2 to 200, more preferably 5 to 150, and still more preferably 10 to 100. If this molar ratio is less than 2, the transparency of the cured product tends to deteriorate, and if it exceeds 200, the hardness of the cured product tends to be insufficient.
  • the water used for hydrolysis of the inorganic oxide precursor (a) in the above reaction may be added all at once, dividedly, or added dropwise.
  • the temperature at which the inorganic oxide (A) is produced by the above reaction is preferably 40 to 80 ° C., more preferably 60 to 70 ° C. When the temperature is 40 ° C. or higher, the reaction rate is increased, and thus productivity is improved. Moreover, polycondensation of the hydrolyzate of an inorganic oxidation precursor (a) can be advanced, without polyfunctional (meth) acrylate superposing
  • the reaction time for producing the inorganic oxide (A) by the above reaction is preferably 30 minutes to 6 hours, more preferably 2 hours to 4 hours.
  • the curable resin composition (C) of the present invention has a total light transmittance of 90% or more, a cured product having excellent transparency can be provided.
  • the haze value of the cured product of the curable resin composition (C) of the present invention is preferably 1% or less. If it exceeds 1%, the transparency of the cured product deteriorates.
  • the haze value of the cured product is measured with a total light transmittance measuring device in accordance with JIS-K7105 for a cured film of the curable resin composition as will be described in detail in the measurement method of the examples.
  • the median diameter d of the inorganic oxide (A) measured by the dynamic light scattering method is preferably 1 to 100 nm, more preferably 10 to 50 nm.
  • the median diameter d of the inorganic oxide (A) exceeds 100 nm, transparency and hardness may be deteriorated, and when it is less than 1 nm, the hardness of the cured product may be insufficient.
  • the curable resin composition (C) contains the inorganic oxide (A) in which the median diameter d of the particles measured by the dynamic light scattering method is in the above range, a cured product having high transparency and hardness can be formed. .
  • composition containing an inorganic oxide (A) obtained by reacting an inorganic oxide precursor (a) with water contains a polyfunctional (meth) acrylate (B) and is used as a curable resin composition (C). can do.
  • the same kind of polyfunctionality as the polyfunctional (meth) acrylate (B) used in the production of the inorganic oxide (A) It is good also as a curable resin composition (C) by further adding and diluting (meth) acrylate (B) or a different kind of (B).
  • the catalyst (b) may or may not be removed from the composition containing the inorganic oxide (A) and the polyfunctional (meth) acrylate (B). You may neutralize.
  • Examples of the energy source used when curing the curable resin composition of the present invention include heat, electron beam, and X-ray.
  • the energy source is also cured, but the photopolymerization initiator (D) is further added. By containing, it can be cured by light irradiation.
  • ultraviolet rays, infrared rays, and visible rays can be used as the rays. Of these, ultraviolet rays and electron beams are preferable from the viewpoints of curability and resin deterioration.
  • the curable resin composition (C) of the present invention is suitably used as an active energy ray-curable resin composition that is cured by active energy rays (ultraviolet rays, electron rays, X rays, etc.) in this way.
  • active energy rays ultraviolet rays, electron rays, X rays, etc.
  • the curable resin composition (C) of the present invention preferably further contains a photopolymerization initiator (D).
  • a photopolymerization initiator (D) added to the curable resin composition (C) of the present invention include a phosphine oxide compound (D1), a benzoylformate compound (D2), a thioxanthone compound (D3), and an oxime.
  • Examples include ester compounds (D4), hydroxybenzoyl compounds (D5), benzophenone compounds (D6), ketal compounds (D7), 1,3 ⁇ aminoalkylphenone compounds (D8), and the like.
  • Examples of the phosphine oxide compound (D1) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,3,5-trimethylbenzoyldiphenylphosphine. Examples include oxides.
  • Examples of the benzoylformate compound (D2) include methylbenzoylformate.
  • Examples of the thioxanthone compound (D3) include isopropyl thioxanthone.
  • Examples of the oxime ester compound (D4) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1 (O-acetyloxime) and the like.
  • Examples of the hydroxybenzoyl compound (D5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and benzoin alkyl ether.
  • Examples of the benzophenone compound (D6) include benzophenone.
  • Examples of the ketal compound (D7) include benzyl dimethyl ketal.
  • Examples of the 1,3 ⁇ aminoalkylphenone compound (D8) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
  • photopolymerization initiators (D) from the viewpoint of pencil hardness, (D1), (D5), and (D8) are preferred, and bis (2,4,6-trimethylbenzoyl) is more preferred.
  • -Phenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,3,5-trimethylbenzoyldiphenylphosphine oxide is there.
  • the content of the photopolymerization initiator (D) is curable and transparent. From the viewpoint, it is 0.1 to 10% by weight, preferably 0.2 to 7% by weight.
  • the curable resin composition (C) of the present invention may contain one or more various additives as long as the effects of the present invention are not impaired.
  • the additive include a plasticizer, an organic solvent, a dispersant, an antifoaming agent, a thixotropy imparting agent (thickening agent), a slip agent, an antioxidant, a hindered amine light stabilizer, and an ultraviolet absorber.
  • the curable resin composition (C) of the present invention can be a paint diluted with a solvent as necessary in order to adjust the viscosity to be suitable for coating during coating.
  • the amount of the solvent used is usually 2,000% or less, preferably 10 to 500%, based on the total weight of the curable resin composition.
  • the viscosity of the coating is usually 5 to 5,000 mPa ⁇ s at the temperature during use (usually 5 to 60 ° C.), and preferably 50 to 1,000 mPa ⁇ s from the viewpoint of stable coating.
  • the solvent is not particularly limited as long as it dissolves the resin component in the curable resin composition of the present invention.
  • aromatic hydrocarbons eg toluene, xylene and ethylbenzene
  • esters or ether esters eg ethyl acetate, butyl acetate and methoxybutyl acetate
  • ethers eg diethyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, monomethyl ether of propylene glycol and monoethyl ether of diethylene glycol
  • ketones eg acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone
  • alcohols eg methanol, ethanol, n- or i-propanol
  • esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferable from the viewpoint of smoothness of the coating film and solvent removal efficiency, and more preferable are ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof. It is.
  • the curable resin composition (C) of the present invention is diluted with a solvent if necessary, applied to at least a part of at least one side of the substrate, and dried if necessary.
  • a hard coat coating having a cured film can be obtained by curing with irradiation or heat of X-rays or the like.
  • a coating machine bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.
  • the coating film thickness is usually 0.5 to 300 ⁇ m as the film thickness after curing and drying.
  • the upper limit is preferably 250 ⁇ m from the viewpoints of drying properties and curability, and the lower limit is preferably 1 ⁇ m from the viewpoints of wear resistance, solvent resistance, and contamination resistance.
  • the transparent substrate examples include those made of resins such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, and polycycloolefin.
  • resins such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, and polycycloolefin.
  • the curable resin composition (C) of the present invention When the curable resin composition (C) of the present invention is used after being diluted with a solvent, it is preferably dried after coating.
  • the drying method include hot air drying (such as a dryer).
  • the drying temperature is usually 10 to 200 ° C., the upper limit is preferably 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and the lower limit is preferably 30 ° C. from the viewpoint of the drying speed.
  • UV irradiation devices for example, ultraviolet irradiation devices [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.] can be used.
  • the lamp to be used include a high-pressure mercury lamp and a metal halide lamp.
  • the irradiation amount of ultraviolet rays is preferably 10 to 10,000 mJ / cm 2 , more preferably 100 to 5,000 mJ / cm 2 from the viewpoint of the curability of the curable resin composition and the flexibility of the cured product.
  • the method for producing a curable resin composition (C) of the present invention is a method for producing a curable resin composition (C) containing an inorganic oxide (A) and a polyfunctional (meth) acrylate (B).
  • the polyfunctional (meth) acrylate (B) in the presence of the catalyst (b), one or more selected from the group consisting of inorganic alkoxide (a1), metal inorganic acid salt (a2) and inorganic chloride (a3)
  • Such a manufacturing method is preferable as a manufacturing method of the curable resin composition (C) of the present invention described above.
  • the step of obtaining the inorganic oxide (A) and preferred embodiments thereof are the same as those in the production of the inorganic oxide (A) described above.
  • the molar ratio of the inorganic oxide precursor (a) / water is preferably 2 to 200, more preferably 5 to 150, and still more preferably 10 to 100.
  • the catalyst (b), the inorganic alkoxide (a1), the metal inorganic acid salt (a2) and the inorganic chloride (a3) used as the inorganic oxide precursor (a) are the same as described above.
  • the inorganic oxide (A) and the polyfunctional (meth) acrylate (B) are the same as those in the curable resin composition (C) described above.
  • the polyfunctional (meth) acrylate (B) preferably contains a polyfunctional (meth) acrylate having a reactive group ( ⁇ ) capable of reacting with a hydroxyl group, and has a reactive group ( ⁇ ) capable of reacting with a hydroxyl group. More preferably, it is a polyfunctional (meth) acrylate.
  • the composition containing the inorganic oxide (A) and the polyfunctional (meth) acrylate (B) obtained in the step of obtaining the inorganic oxide (A) is a curable resin composition of the present invention.
  • (C) can be used.
  • the inorganic oxide (A) and the polyfunctional ( In the composition containing (meth) acrylate (B), polyfunctional (meth) acrylate (B) of the same type as polyfunctional (meth) acrylate (B) used for the production of inorganic oxide (A) or different types (B) may be further added and diluted to obtain a curable resin composition (C).
  • Production Examples 2-6 The inorganic alkoxide (a), catalyst (b) and water shown in Table 1 were reacted in the respective polyfunctional (meth) acrylates (B) in the same manner as in Production Example 1 to give the corresponding inorganic oxides (A- A solution of (meth) acrylates 2) to (A-6) was obtained.
  • Comparative production example 1 The reaction was carried out in the same manner as in Production Example 1 with the number of parts shown in Table 1 to obtain a solution of the corresponding inorganic oxide (A′-1) in (meth) acrylate.
  • This is an inorganic oxide solution for Comparative Example 1 in that monofunctional (meth) acrylate (B′-1) is used.
  • Comparative production example 2 The reaction was carried out in the same manner as in Production Example 1 with the number of parts shown in Table 1 to obtain a solution of the corresponding inorganic oxide (A′-2) in (meth) acrylate. This is the inorganic oxide solution for Comparative Example 2 in terms of the content of inorganic oxide.
  • the raw materials used in Table 1 are as follows.
  • Example 1 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 103.87 parts of the solution obtained in Production Example 1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1 part of 1-one (D-2) [trade name “Irgacure 907”, manufactured by BASF Corp.] was added and mixed and stirred at 65 ° C. until uniform, to obtain a curable resin composition (C-1).
  • Example 2 As in Example 1, the solutions obtained in Production Examples 2 to 6 and Comparative Production Examples 1 and 2 and the photopolymerization initiator (D) were uniformly mixed in the number of parts shown in Table 2, and the corresponding curable resin composition was obtained. The products (C-2) to (C-6) and (C′-1) to (C′-2) were obtained. In the solutions obtained in Production Examples 1 to 6 and Comparative Production Examples 1 and 2, the inorganic oxide (A) and the polyfunctional (meth) acrylate (B) (or monofunctional (meth) acrylate (B ′)) were used. The number of copies shown in the above is included.
  • Comparative Examples 3-4 In Comparative Examples 3 and 4, instead of synthesizing the inorganic oxide (A) in the polyfunctional (meth) acrylate (B) as in the above production example, the number of parts shown in Table 2 is a commercially available inorganic oxide. Fine particles (A′-3) are blended in the polyfunctional (meth) acrylate (B) simultaneously with the photopolymerization initiator (D) so as to be 30% by weight and 10% by weight, respectively. '-3) to (C'-4) were obtained.
  • D-1 1,3,5-trimethylbenzoyldiphenylphosphine oxide [trade name “Lucirin TPO”, manufactured by BASF Corporation]
  • D-2) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [trade name “Irgacure 907”, manufactured by BASF Corporation]
  • the content of the inorganic oxide (A) in Table 2 is the content (% by weight) of the inorganic oxide (A) in the curable resin composition.
  • the (meth) acrylate solutions of inorganic oxides used for the preparation of the curable resin compositions (C-1) to (C-6) and (C′-1) to (C′-2) are shown in Table 2.
  • polyfunctional (meth) acrylate (B) or monofunctional (meth) acrylate (B ′)
  • (B) is included in parts by weight shown in Table 1.
  • tetraethoxysilane reactants (A-1) to (A-2), tetra-n-butoxytitanium reactant (A-3), tetraethoxysilane reactants (A-4) to (A-6) Are the inorganic oxides (A-1) to (A-6) produced in Production Examples 1 to 6, respectively.
  • the tetraethoxysilane reactants (A′-1) to (A′-2) are inorganic oxides (A′-1) to (A′-2) produced in Comparative Production Examples 1 and 2, respectively.
  • Curable resin compositions (C-1) to (C-6) and (C′-1) to (C′-4) were each diluted with methyl ethyl ketone using a disperser to prepare a non-volatile content of 40%.
  • the diluted liquid of the curable resin composition was applied to one side of a TAC film (triacetyl cellulose film) substrate having a thickness of 40 ⁇ m so that the film thickness after drying and curing was 7 ⁇ m.
  • an ultraviolet irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd. same as below. ] was irradiated with ultraviolet rays of 300 mJ / cm 2 under a nitrogen atmosphere to produce a film having a cured film on the surface of the base film.
  • the curable resin compositions of Examples 1 to 6 of the present invention do not impair the transparency of the composition even when containing a large amount of inorganic oxide fine particles, and the cured product has high hardness.
  • the comparative example 1 which uses only a monofunctional acrylate has inferior pencil hardness.
  • Comparative Example 2 in which the content of the inorganic oxide (A) is less than 25% by weight, the pencil hardness is insufficient.
  • Comparative Example 3 obtained by a method of adding commercially available silica fine particles simultaneously with the polyfunctional (meth) acrylate (B) and containing 30% by weight of silica fine particles but not satisfying the relational expression (1) is inferior in transparency. . Therefore, in Comparative Example 4 in which the silica fine particles are reduced to an amount (10% by weight) that can ensure transparency, the pencil hardness is insufficient.
  • the hard coat film having a hard coat film obtained by curing the curable composition of the present invention is excellent in pencil hardness and transparency, the surface hardness of a plastic optical component such as a flat panel display or a touch panel, Suitable for fields with excellent transparency.

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Abstract

L'invention concerne une composition de résine durcissable (C) qui est caractéristique en ce qu'elle comprend un oxyde inorganique (A) et un (méth)acrylate polyfonctionnel (B), sa teneur en oxyde inorganique (A) est comprise entre 25 et 80% en masse, sa transmittance de lumière totale est supérieure ou égale à 90%, et l'expression relationnelle (1) suivante est satisfaite. Ｔ≧９１－１,２５×Ｗ／１００ （１）［dans la formule, W représente la teneur (% en masse) d'oxyde inorganique (A) dans la composition de résine durcissable (C), et T représente la transmittance de lumière totale (%) de la composition de résine durcissable (C). ］
PCT/JP2016/065513 2015-05-28 2016-05-25 Composition de résine durcissable, et procédé de fabrication ce celle-ci WO2016190373A1 (fr)

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JP2017043735A (ja) * 2015-08-28 2017-03-02 三洋化成工業株式会社 活性エネルギー線硬化性組成物の製造方法
JP2018150522A (ja) * 2017-03-13 2018-09-27 三洋化成工業株式会社 光硬化性樹脂組成物
JP2021504554A (ja) * 2017-11-21 2021-02-15 オルネクス ベルギー エス エー 無極性基材用の接着促進化合物

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JP7273050B2 (ja) 2017-11-21 2023-05-12 オルネクス ベルギー エス エー 無極性基材用の接着促進化合物

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