WO2019123731A1 - Composition de résine durcissable de type siloxane et liquide de revêtement dur - Google Patents

Composition de résine durcissable de type siloxane et liquide de revêtement dur Download PDF

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Publication number
WO2019123731A1
WO2019123731A1 PCT/JP2018/033187 JP2018033187W WO2019123731A1 WO 2019123731 A1 WO2019123731 A1 WO 2019123731A1 JP 2018033187 W JP2018033187 W JP 2018033187W WO 2019123731 A1 WO2019123731 A1 WO 2019123731A1
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Prior art keywords
group
component
siloxane
resin
carbon atoms
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English (en)
Japanese (ja)
Inventor
佐藤　恵
齋藤　憲
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority claimed from JP2017246132A external-priority patent/JP2019112519A/ja
Priority claimed from JP2018035070A external-priority patent/JP7320922B2/ja
Application filed by Nippon Steel Chemical and Materials Co Ltd filed Critical Nippon Steel Chemical and Materials Co Ltd
Publication of WO2019123731A1 publication Critical patent/WO2019123731A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents

Definitions

  • the present invention relates to a siloxane-based curable resin composition useful as a hard coating liquid excellent in abrasion resistance, transparency, low curling property, and the like.
  • This composition is applicable to various hard coating materials, such as electronic parts, such as a display and a case, an interior of a car, a household appliance member, and a construction member, for example.
  • a member in which the surface of a resin base material is protected with a hard coat material having high scratch resistance has been used as an alternative to metal and glass.
  • a heart coating solution is usually applied to a resin substrate to be protected, and an acrylic composition is often used as such a hard coating solution.
  • Acrylic compositions are generally formed by radical reaction by irradiation of active energy rays such as ultraviolet rays and electron beams, so that they can be cured in a short time at a low temperature, and toughness can be maintained by compounded resin compositions. It is widely used in adhesives and the like.
  • siloxane condensates synthesized under a basic catalyst consist of cage type, random type and ladder type, and most of them are cage type rigid structures, and furthermore, the crosslinked structure by alicyclic epoxy group is also rigid. Because of this, the resulting film has a problem that it is fragile while it is high in hardness.
  • the present invention has been made to solve the above-mentioned problems, and as a hard coating material which can be cured in the atmosphere in a short time and is excellent in scratch resistance and transparency, low curlability, flexibility and the like. It is an object of the present invention to provide a useful curable resin composition and its hard coating solution.
  • this invention is a partial hydrolysis-condensation product which is the partial hydrolysis-condensation product of the following (A) component and (B) component, Comprising: Epoxy equivalent (g / eq) is 200-4000, as the 1st aspect It is a siloxane-based curable resin composition characterized by including: Component (A): an alkoxysilane having an isocyanurate ring structure represented by the following general formula (i) or a partial hydrolytic condensate thereof, (Wherein, R 1 represents an organic group having 1 to 15 carbon atoms, R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 represents an organic group having 1 to 6 carbon atoms, a Represents a number of 0 to 2, and X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii).
  • the siloxane-based curable resin composition preferably has a ratio of component (A) to component (B) of 0.01 to 7 moles of component (A) per 1 mole of component (B).
  • the above-mentioned siloxane-based curable resin composition is a hard coating solution containing a curing catalyst as component (C) and an organic solvent as component (D).
  • a method of forming a hard coating film characterized in that the above-mentioned siloxane-based curable resin composition is applied to an underlayer or a substrate, dried and then cured by active energy ray irradiation or heating. It is. Furthermore, this may be heat-treated.
  • a second aspect of the present invention is a partially hydrolyzed condensate of the above components (A) and (B), which has an epoxy equivalent (g / eq) of 200 to 4000,
  • a siloxane-based curable resin composition comprising: a cationic photopolymerization initiator as the component C '); and a surface conditioner as the component (E): (C ') component; photo cationic polymerization initiator (E) component; a surface conditioner comprising a fluorine compound, a dimethylsiloxane compound, or a modified product or derivative thereof.
  • the siloxane-based curable resin composition preferably has a ratio of component (A) to component (B) of 0.01 to 7 moles of component (A) per 1 mole of component (B).
  • the component (E) is preferably a surface conditioner having a reactive group that forms a covalent bond with the partial hydrolytic condensate of the components (A) and (B).
  • the siloxane-based curable resin composition contains an organic solvent as the component (D).
  • a method of forming a hard coating film is characterized in that the above-mentioned siloxane-based curable resin composition is applied to an underlayer or a substrate and dried, and then cured by active energy ray irradiation. . Furthermore, it is a cured film obtained by curing the above-mentioned siloxane-based curable resin composition.
  • a laminate comprising a base resin layer and a hard resin layer formed from a hard coating solution containing a siloxane-based curable resin, a curing catalyst as component (C), and an organic solvent as component (D). is there.
  • the hard resin layer and the base material may be laminated via a resin layer composed of a single layer or a plurality of layers, and a surface treatment layer may be formed on the base material.
  • a hard coating liquid containing the above-mentioned siloxane-based curable resin composition is applied to a substrate, a resin layer, or a surface-treated substrate, dried and then irradiated with active energy rays or heated. It is a method of producing a hard coating film characterized by curing.
  • a hard siloxane resin layer which consists of a hard coating film can be formed on a substrate layer via a resin layer if needed, and it becomes a layered product by which a hard coating film was formed in the surface.
  • the siloxane-based curable resin composition of the present invention comprises a partial hydrolytic condensate of the components (A) and (B). This partial hydrolytic condensate has an epoxy equivalent of 200 to 4000 (g / eq).
  • the siloxane-based curable resin composition of the present invention may consist only of the above-mentioned partial hydrolysis condensate, or may contain other components.
  • the siloxane-based curable resin composition of the present invention is a curing catalyst for the component (C), a cationic photopolymerization initiator for the component (C '), (C) together with the partial hydrolytic condensates of the components (A) and (B). It is preferable to include the organic solvent of the component D) and the surface conditioner of the component (E), and it may further include components other than the components (A) to (E).
  • the component (A) is an alkoxysilane having an isocyanurate ring structure represented by the above general formula (i) or a partial hydrolysis condensate thereof.
  • the component (A) having an isocyanurate ring structure causes the condensation product or the cured product to have a multi-branched structure, so that it is considered that the bond is extended in three dimensions and the brittleness is improved.
  • R 1 represents an organic group having 1 to 15 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 3 represents an organic group having 1 to 6 carbon atoms.
  • a represents a number of 0 to 2
  • X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii).
  • the common symbols have the same meaning.
  • R 1 , R 2 , R 3 and X are organic groups, they are preferably hydrocarbon groups, more preferably alkyl groups, alkenyl groups and cycloalkyl groups.
  • carbon number is six or more, it may be an aromatic hydrocarbon group.
  • X preferably at least one is a silylalkyl group represented by formula (ii), and more preferably, two of X are all silylalkyl groups represented by formula (ii).
  • a is preferably 0 or 1.
  • the above partial hydrolysis condensate is a dimer or more, and means a condensate having an alkoxysilane group or a hydroxyl group, which is partially dimerized and partially hydrolyzed and partially condensed.
  • completely hydrolyzed condensates are distinguished by the fact that the hydroxyl groups are almost consumed by the condensation reaction and the condensation reaction does not proceed any further.
  • alkoxysilane having an isocyanurate ring structure represented by the general formula (i) examples include 1,3,5-tris (methyldimethoxysilylpropyl) isocyanurate and 1,3,5-tris (methyldiethoxysilyl).
  • 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (methyldiethoxysilylpropyl) isocyanurate, 1,3,5-tris (trimethoxysilylpropyl) isocyanate A nurate, 1,3,5-tris (trimethoxysilylethyl) isocyanurate.
  • the component (B) is a siloxane resin which is an alkoxysilane having an epoxy group or an oxetane group represented by the above formula (iii) or a partial hydrolysis condensate thereof. It is considered that the scratch resistance and storage stability are improved by the component (B) having an epoxy group or an oxetane group.
  • R 4 is an organic group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, which contains an epoxy group or an oxetane group.
  • R 5 is an organic group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, which contains neither an epoxy group nor an oxetane group.
  • R 6 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.
  • the organic group in R 4 and R 5 is preferably an alkyl group, and the organic group in R 4 is preferably an alkyl group having a glycidyl group, an alicyclic epoxy group and an oxetane group at the end.
  • the calculation of the carbon number of the organic group in R 4 does not include the carbon number of the epoxy group or the oxetane group. When it contains the carbon number which an epoxy group or an oxetane group has, 2 to 3 are added to the said carbon number.
  • b and c each represent a number (average value) of 0 ⁇ b ⁇ 1 and 0 ⁇ c ⁇ 2, and b + c satisfies 0 ⁇ b + c ⁇ 2.
  • 4-b-c is preferably a number of 2 or 3.
  • b is preferably 0.1 or more.
  • alkoxysilane having an epoxy group or an oxetane group represented by the formula (iii) examples include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutyltrimethoxy, for example.
  • 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl) methoxy] propyltrimethoxysilane is there.
  • the partial hydrolysis condensate of the alkoxysilane of Formula (iii) is obtained by carrying out the partial hydrolysis of this like the alkoxysilane of Formula (i).
  • the blending ratio (molar ratio) is preferably 0.01 to 7 moles, and more preferably 0.01 to 1.5 moles, per 1 mole of the component (B).
  • the partial hydrolysis condensates of the components (A) and (B) are partial hydrolysis condensates of a mixture containing the components (A) and (B).
  • the mixture containing the component (A) and the component (B) can contain other silane compounds or (partial) hydrolysates thereof unless the object of the present invention is inhibited.
  • silane compounds for example, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane , Octyltriethoxysilane, decyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltriol Methoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysi
  • the partial hydrolysis condensates of the components (A) and (B) are partial hydrolysis condensates of a mixture containing the components (A) and (B).
  • the hydrolysis is preferably performed to such an extent that all of the alkoxy groups are hydrolyzed to become OH groups, but the condensation to form a siloxane bond by condensation of Si—OH groups is in a state of being partially performed. If condensation proceeds too much, it gels and can not be dissolved or dispersed in a solvent. Further, after partially hydrolyzing the components (A) and (B) alone, they may be mixed and further subjected to hydrolysis and condensation.
  • hydrolytic condensates are siloxane resins, and the average molecular weight (Mw) thereof is preferably 300 to 60000, more preferably 400 to 30000.
  • the partial hydrolytic condensates of components (A) and (B) have an epoxy group or an oxetane, and have an epoxy equivalent of 200 to 4000, preferably 200 to 1000, and more preferably 200 to 500.
  • the molecular weight can also be calculated from this epoxy equivalent.
  • the partial hydrolytic condensate does not contain the catalyst or solvent added during hydrolysis, water which remains unreacted, water produced by condensation, and only the Si-containing compound produced by partial hydrolytic condensation, It is a so-called siloxane resin component. If the epoxy equivalent (g / eq) is less than the lower limit of the epoxy equivalent, scratch resistance and storage stability will be reduced. When the epoxy equivalent exceeds the upper limit, the resulting film becomes brittle and the toughness decreases.
  • the epoxy equivalent refers to the mass of a siloxane resin having one equivalent of an epoxy group, and does not include the mass of a solvent or the like.
  • (B) component does not have an epoxy group but has an oxetane group
  • an oxetane equivalent becomes the same value as an epoxy equivalent, it can be understood as an epoxy equivalent.
  • a general purpose bifunctional epoxy resin such as bisphenol type epoxy resin or a multifunctional epoxy resin such as phenol novolac epoxy resin can be used.
  • the solution in order to obtain a linear siloxane structure, the solution may be hydrolyzed with acidic water of pH 1 to 7, preferably pH 2 to 5.
  • acidic water of pH 1 to 7, preferably pH 2 to 5.
  • an organic acid such as hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, toluenesulfonic acid or the like
  • Inorganic acids can be used.
  • the amount of the acid or acid catalyst used is preferably 0.0001 to 20% by weight with respect to the product (partially hydrolyzed condensate).
  • the hydrolysis reaction requires the presence of water.
  • the amount of water may be an amount sufficient to hydrolyze (part of) the hydrolyzable group in the above silane compound, and may be 0.5 to 0.5 of the theoretical amount (mol) of the number of hydrolyzable groups. Preferably, the amount corresponds to 2.0 times mol. More preferably, it is 0.7 to 1.5 times mol. Also, if the acid or catalyst is added as an aqueous solution, add that water to the calculation. When the amount of water is small, sufficient hydrolysis does not proceed, and when the amount is large, the remaining water reduces the coating property and the drying efficiency.
  • the dehydration condensation reaction of the silanol group generated simultaneously with the hydrolysis occurs to form a siloxane resin composition.
  • the temperature at which this condensation is performed is normal temperature or heating at 120 ° C. or less, more preferably 30 ° C. or more and 100 ° C. or less. When the temperature is low, the time for hydrolysis and condensation reaction is long, the productivity is low, and when the temperature is high over the range, there is a possibility of insolubilization.
  • Various organic solvents may be mixed in order to adjust the reaction rate of the above hydrolysis and condensation and the molecular weight of the resin composition to be produced.
  • alcohols such as methanol, ethanol, butanol, isobutanol, isopropyl alcohol, propanol, t-butanol, sec-butanol, benzyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone
  • diacetone alcohol and ester include ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate and ethers.
  • the amount of the organic solvent mixed is preferably 10 parts by weight to 2000 parts by weight, based on 100 parts by weight of the total amount of the components to be hydrolyzed.
  • the compounding quantity of (B) component is large, it can also hydrolyze and condense by the non-solvent which does not use an organic solvent.
  • the resin composition in the first aspect of the present invention may be only the above-mentioned partial hydrolysis condensate, but the partial hydrolysis condensate has an epoxy group or an oxetane group and is also epoxy resins, so It is good to mix
  • a curing catalyst (C) a curing agent (acid generator or base generator) capable of generating an acid or a base by heating or active energy ray irradiation, or a curing accelerator can be applied.
  • Examples of the curing agent that generates an acid or a base include diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, and ammonium salts.
  • Specific examples of the heat or photoacid generator include San-Aid SI series (manufactured by Sanshin Chemical Co., Ltd.), TA or CPI series (manufactured by San-Apro), Adeka Ark SP Series (manufactured by ADEKA), WPI series (Japanese An example can be manufactured by Mitsuko Junyaku Co.).
  • the photobase generator examples include WPBG series (manufactured by Wako Pure Chemical Industries, Ltd.), O0395, A2502 (manufactured by Tokyo Kasei Kogyo Co., Ltd.), EIPBG (manufactured by I-Bite KK), and the like.
  • a photosensitizer or a photosensitizer such as a radical polymerization initiator which exhibits an effect in combination may be used in combination.
  • amine adducts, hydrazides and imidazoles may be mentioned.
  • Amicure PN series (manufactured by Ajinomoto Fine Techno Co., Ltd.), Fujicure-FXR series (manufactured by TOKA), an imidazole compound series (manufactured by Shikoku Kasei Co., Ltd.), and the like can be exemplified.
  • the addition amount of the component (C) is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the partial hydrolysis condensate of the components (A) and (B). If it is less than this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface height can not be obtained. Even if added beyond this range, no further improvement in the reaction rate can be expected.
  • the partial hydrolytic condensates of the (A) component and the (B) component have an epoxy group or an oxetane group and are also epoxy resins, so they are cured
  • the photocationic polymerization initiator of the above is blended as the component (C ').
  • the photo cationic polymerization initiator (C ') is also an acid generator which generates an acid (cation) upon irradiation with active energy rays. Examples include diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts, and ammonium salts.
  • the above-mentioned San Aid SI series (manufactured by Sanshin Chemical Co., Ltd.), TA or CPI, IK series (manufactured by San Apro), Adeka Ark SP series (manufactured by ADEKA), WPI series (manufactured by Wako Pure Chemical Industries, Ltd.) ), Irgacure series (manufactured by BASF), etc. correspond to this.
  • iodonium salts are preferable when thick films and transparency are required.
  • IK-1 manufactured by San-Apro
  • WPI 113 manufactured by San-Apro
  • WPI 116 manufactured by Wako Pure Chemical Industries, Ltd.
  • WPI 170 manufactured by Wako Pure Chemical Industries, Ltd.
  • WPI 124 manufactured by Wako Pure Chemical Industries, Ltd.
  • Irg 250 manufactured by BASF
  • a photosensitizer or a photosensitizer such as a sensitizer and a radical polymerization initiator which exhibit an effect in combination with the initiator may be used in combination.
  • the addition amount of the component (C ') is preferably 0.1 to 100 parts by weight of the partial hydrolytic condensate of the components (A) and (B), similarly to the curing catalyst of the component (C). It is in the range of 10 parts by weight, more preferably 1 to 7 parts by weight. If it is less than this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface height can not be obtained. Even if added beyond this range, no further improvement in the reaction rate can be expected.
  • blends with the surface conditioner (E) component mentioned later the abrasion resistance can be further improved by setting it as 1 weight part or more of range.
  • the resin composition in the second aspect of the present invention contains a surface conditioner of component (E).
  • the surface control agent is blended for the purpose of improving the leveling property and scratch resistance at the time of film formation.
  • the surface conditioner fluorine compounds, dimethylsiloxane compounds, or modified products or derivatives of these compounds (including oligomers and polymers) are used. Specifically, FZ-2123, 57 ADDITIVE (made by Toray Dow Corning), KP124, KP109, KP110, KP121, KP106, KP112 (made by Shin-Etsu Chemical Co., Ltd.), BYK306, BYK307, BYK307, BYK310, BYK313, BYK333, BYK342.
  • a structure having a reactive group incorporated in the crosslinks of partial hydrolytic condensates of the (A) component and the (B) component is preferable.
  • reactive groups include hydroxyl groups such as carbinol groups and silanol groups, or epoxy groups and mercapto groups, and fluorine compounds and dimethylsiloxane compounds modified with these reactive groups are more preferable.
  • L-7604, 8029 ADDITIVE, 8054 ADDITIVE, 8211 ADDITIVE, 8526 ADDITIVE manufactured by Toray Dow Corning
  • BYK 370, BYK 375, BYK 377, BYK SILCEAN 3700, BYK SILCEAN 3701, BYK SILCEAN 3720 manufactured by BYK
  • the amount of component (E) added is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight per 100 parts by weight of the partial hydrolysis condensate of components (A) and (B). It is a range of parts by weight. If this range is not reached, it is not possible to improve the leveling property and the scratch resistance at the time of film formation. Even if it is added beyond this range, no further improvement can be expected, but there is a possibility that other physical properties may be inhibited.
  • the siloxane-based curable resin composition of the present invention can be made into a hard coating solution by containing an organic solvent as the component (D).
  • Component (D) is an organic solvent.
  • an organic solvent the same thing as the organic solvent mixed at the time of hydrolysis can be illustrated, and it may be the same as or different from the solvent mixed at the time of hydrolysis.
  • the compounding amount of the component (D) is preferably 10 parts by weight to 5000 parts by weight, and more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the partial hydrolysis condensate.
  • the compounding quantity of (D) component is the quantity also including the quantity of the solvent mixed at the time of hydrolysis.
  • a hard coating solution containing the above-mentioned components it is desirable to apply a hard coating solution containing the above-mentioned components on a substrate or a primer layer, dry it, and then light cure it by ultraviolet irradiation.
  • This curing is caused by polymerization of an epoxy group or an oxetane group, and also contributes to a crosslinking reaction by an addition reaction of an epoxy group or an oxetane group with a silanol group and a condensation of a silanol group.
  • a heating and curing step may be provided in order to sufficiently advance condensation of silanol groups.
  • epoxy resin acrylic resin, organic / inorganic filler, plasticizer, flame retardant, heat stabilizer, antioxidant, ultraviolet absorber, ultraviolet shielding agent, lubricant, antistatic agent, mold release agent, foaming
  • resin components such as other siloxane-based resins, organic acrylates or vinyl compounds can be exemplified for the purpose of promoting the reaction, agents, nucleating agents, colorants, crosslinking agents, dispersing aids, and the like.
  • an acrylic resin or an organic acrylate it is preferable to use a photo radical polymerization initiator in combination, and it is desirable to blend an acrylic group-containing fluorine compound or a dimethylsiloxane compound or a modified product thereof as a surface control agent.
  • a method of forming a hard coating film there may be mentioned, for example, a flow coating method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method and a dipping method.
  • coating film thickness is adjusted with solid content concentration in consideration of the formed film thickness after hardening by irradiation of an active energy ray, drying.
  • the solvent is preferably removed by drying or the like.
  • the drying temperature is set to a condition that the base material used is not deformed, and the drying time is preferably 1 hour or less from the viewpoint of productivity.
  • the thickness of the hard coating is 0.5 to 20 ⁇ m, preferably 1 to 10 ⁇ m.
  • the hard coating film forming step in the case of using a photoactive curing catalyst, it is preferable to irradiate the active energy ray under the conditions of an illuminance of 100 mW / cm 2 or more and an integrated light amount of 1000 mJ / cm 2 or more.
  • an illuminance 100 mW / cm 2 or more
  • an integrated light amount 1000 mJ / cm 2 or more.
  • the curing temperature is set so as not to deform the base material to be used, to accelerate the hydrolysis and condensation of the siloxane resin, and further to diffuse the generated acid or base to accelerate the curing reaction of the epoxy group or the oxetane group.
  • the temperature condition is 70 to 150 ° C., preferably 80 to 120 ° C.
  • the laminate as the third aspect of the present invention is obtained by forming a hard siloxane resin layer as a hard coating film on a base material layer, optionally through another resin layer.
  • the hard coating film is formed from a hard coating liquid containing a siloxane-based curable resin containing the partial hydrolytic condensate of the components (A) and (B), a curing catalyst (C) and an organic solvent (D). .
  • thermoplastic resin polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, polymethyl methacryl, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyamide, polyacetal, polyphenylene ether , Polycarbonate, polybutylene terephthalate, polyvinylidene fluoride, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyamide imide, polyether imide, polyether ether ketone, polyimide, liquid crystal polymer, polytetrafluoroethylene, cycloolefin copolymer, elastomer Etc.
  • a thermoplastic resin polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, polymethyl meth
  • the curable resin examples include phenol resin, urea resin, melamine resin, polyester resin, acrylic resin, urethane resin, epoxy resin, imide resin, siloxane resin, fluorine resin and the like.
  • steel plates such as aluminum, magnesium, copper, iron, such alloy steel plates, and various plated steel plates are mentioned.
  • wood such as zelkova, hinoki, cedar, red pine, abozilla, rosewood, walnut, teak, mahogany, white oak, iron wood, cherry, beech, maple, rubber wood, chestnut, walnut, leek, tuna, pine, pine, etc.
  • wood such as zelkova, hinoki, cedar, red pine, abozilla, rosewood, walnut, teak, mahogany, white oak, iron wood, cherry, beech, maple, rubber wood, chestnut, walnut, leek, tuna, pine, pine, etc.
  • wood such as zelkova, hinoki, cedar, red pine, abozilla, rosewood, walnut, teak, ma
  • Examples of paper include wood derived from artificial cellulose fiber, eucalyptus, acacia and the like, non-wood derived from hemp, kozo, bamboo and the like, and a composite of this with inorganic fine particles or a resin Etc.
  • Examples of the glass include various glasses such as float glass, tempered glass, heat resistant glass, fire prevention glass, design glass, color glass, laminated glass, heat ray reflective glass and the like.
  • the stone include natural stones such as igneous rock, sedimentary rock, metamorphic rock and artificial marble.
  • a single layer or plural resin layers may be interposed between the hard resin layer and the substrate for the purpose of imparting functionality such as adhesiveness and weather resistance or design property, and this resin layer is a single layer
  • a curable resin such as a commercially available primer material, an adhesive, or a printing material suitable for the base material in the case of a plurality of layers in the case of a plurality of layers
  • the resin include acrylic resin, urethane resin, polyurea resin, epoxy resin, phenol resin, siloxane resin, polyimide resin, and polyamideimide resin. Specific examples of the resin species of the resin layer are given below, but are not particularly limited.
  • acrylic resin a cured resin obtained by curing an acrylic composition containing a polyfunctional acrylic monomer having a molecular weight of 500 or less is preferable.
  • polyfunctional acrylic monomers include polyfunctional (meth) acrylates.
  • polyfunctional acrylates having two or three (meth) acrylic groups in the molecule are preferable, and aliphatic acrylates, alicyclic acrylates, epoxy An acrylate etc. are mentioned.
  • the acrylic composition containing a polyfunctional acrylic monomer it is desirable to contain the compound which has an epoxy group, and it is more preferable that it is epoxy group containing polyfunctional acrylic monomers, such as an epoxy acrylate.
  • polyfunctional (meth) acrylate examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, and tetraethylene.
  • the urethane acrylate etc. which were made to react the acrylate which it has are mentioned.
  • These (meth) acrylates may be used alone or in combination of two or more.
  • a photopolymerization initiator as a polymerization initiator, and the addition amount thereof is 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the resin composition. It is preferable that it is a range. If it is less than this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface height can not be obtained. On the contrary, if the content is beyond this range, further improvement of the reaction rate can not be expected.
  • urethane resin examples include cured resins of aliphatic or aromatic polyester polyol compounds and di, tri or polyisocyanate compounds or melamine resins.
  • polystyrene resin examples include polyester polyols obtained by polycondensation of polybasic acid and polyhydric alcohol, polyester polyols obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone, ⁇ -valerolactone, ethylene oxide, propylene oxide And an alkylene oxide such as butylene oxide, a polymer of a cyclic ether such as tetrahydrofuran or an alkyl-substituted tetrahydrofuran, or a polyether polyol which is a copolymer of two or more of these.
  • polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexame Triisocyanate, bicycloh
  • the urethane resin may have a reactive group in addition to the above-mentioned reactive group, and examples thereof include an amino group, a (meth) acrylate group, a vinyl group, a mercapto group and an epoxy group.
  • polyurea resins include cured resins of polyamine and polyisocyanate.
  • polyamines include aliphatic amines, aromatic amines, modified amines, which have at least two amino groups and may be primary amines, secondary amines, and tertiary amines.
  • 1,2-diaminopropane 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,2-diaminocyclohexane, 1,6-diaminohexane, 1,11-diaminoundecane 1,12-diaminododecane, 3- (cyclohexylamino) propylamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 3,3 '-Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-[1,4-butanediylbis- (oxy) bis] -1-propanamine, menthane diamine, diethylenetriamine, dipropylenetriamine, bis (hexamethylene) Triamine, diethylene tetraamine
  • the epoxy resin examples include curable resins obtained by curing an epoxy resin having at least two epoxy groups with an isocyanate or melamine resin, and known epoxy group-containing resins such as aliphatic epoxy, aromatic epoxy, modified epoxy and the like It can be used. Specifically, bisphenol epoxy resin, novolac epoxy resin, aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, glycidyl ester epoxy resin and the like can be mentioned.
  • bisphenol-type epoxy resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AD-type epoxy resins, bisphenol S-type epoxy resins, etc., and brominated products and water additives thereof.
  • novolac epoxy resins examples include phenol novolac epoxy resins and cresol novolac epoxy resins.
  • aromatic epoxy resin examples include trisphenol methane triglycidyl ether and the like.
  • modified epoxy resin an epoxy ester resin in which a drying oil fatty acid is reacted with a part of the epoxy group of the epoxy group-containing resin, and a polymerizable non-polymerizable resin containing acrylic acid or methacrylic acid in the epoxy group of various epoxy group-containing resins.
  • the polyoxyalkylene modified epoxy group containing resin etc. can be mentioned.
  • a phenol resin although a novolak type resin and a resol type are mentioned, a resol type is preferable, and using together with an epoxy resin is preferable.
  • the siloxane resin is a curable resin such as a ladder type, random type, cage type, ladder type or the like in which one or more siloxane bonds not included in the claims of the present invention are bonded, and alkoxy group containing siloxane, silanol group containing Siloxane, (meth) acrylic group-containing siloxane, epoxy group-containing siloxane, mercapto group-containing siloxane, amino group-containing siloxane, styryl group-containing siloxane, isocyanate group-containing siloxane, ureido group-containing siloxane, vinyl group-containing siloxane, sulfide group-containing siloxane, etc. Can be mentioned. These reactive functional groups may be used alone or in combination of two or more.
  • polyimide resin a resin derived from an acid anhydride and an aromatic diamine, a resin derived from an acid anhydride and an aliphatic diamine, or two or more of these may be used in combination, and when there are a plurality of resin layers In order to prevent the appearance of the base layer or the base material from being damaged, a transparent polyimide resin is preferable.
  • diamines m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylether, 1,3-bis (4-aminophenoxy) benzene, 4,4'-diamino Diphenylsulfone, 2,2-bis (4-aminobenzyloxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4'-diaminobenzanilide, 9,9-bis (4-amino) Phenyl) fluorene etc. are mentioned.
  • the resin composition used for the resin layer may use a photopolymerization initiator, a photoacid generator, and a photobase generator in combination in the case of photocuring in order to accelerate the curing.
  • a thermal polymerization initiator it is preferable to use a thermal polymerization initiator, a thermal acid generator, an amine-based curing agent, a caprolactone-based curing agent, and the like in combination.
  • the compounding amount of these curing accelerators is preferably 0.1 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition.
  • the resin composition used for the resin layer is preferably dissolved in a solvent and applied as a solution to a base material or the like to form a layer, and then cured.
  • the solvent include organic solvents for the purpose of adjusting the solid content concentration, improving the dispersion stability, improving the coatability, and improving the adhesion to the substrate.
  • alcohols such as methanol, ethanol, butanol, isobutanol, isopropyl alcohol, propanol, t-butanol, sec-butanol, benzyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone
  • diacetone alcohol and ester include ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate and ethers.
  • the method of forming the resin layer on the substrate can be formed by applying a solution of various resins and drying, and then either heating or irradiation with active energy rays.
  • crosslinking is formed so as not to cause white turbidity or elution in the hard coating film forming step to be applied later, and it is preferable that the crosslinking not be completely formed.
  • a method of forming a resin layer for example, a flow coating method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method and a dipping method can be mentioned.
  • a coating film thickness is adjusted with solid content concentration in consideration of the formation film thickness after drying and hardening.
  • the resin layer may be mixed with a thermoplastic resin, rubber particles, and the like for the purpose of improving flexibility, adhesion, and the like.
  • the compounding amount is preferably in a range that does not impair the curability of the curable resin, and it is desirable that the thermoplastic resin is 0 to 50 parts by weight with respect to 100 parts by weight of the curable resin.
  • the substrate may be surface-treated to form a surface-treated layer.
  • the surface treatment of the substrate is performed for the purpose of imparting adhesiveness by a hard resin layer or a resin layer and a chemical bonding, or an anchor effect due to electrostatic bonding or unevenness, and general anchor treatment and coupling Agent treatment, ultraviolet irradiation treatment, plasma treatment, corona discharge treatment, blast treatment, brush treatment, polishing treatment, etching treatment, chemical conversion treatment, anodization and the like.
  • the resin base material may be provided with various wiring such as a thin film of an inorganic material that imparts metallic luster, an electronic circuit, etc., as necessary.
  • the laminate of the present invention has a hard coating film composed of a hard siloxane resin layer on the surface, is excellent in scratch resistance and transparency, and can be formed by atmospheric curing in a short time, so it is applied to various applications. it can.
  • displays such as touch panels, conductive films, antireflective films, reflective films, diffusion films, shatterproof films, protective films, front plates, housings, buttons, sensors, electronic device members, windows, instrument panels, Exterior parts, partition windows, windshields, head lamps, condensers, insulation films, heat ray shielding films, vehicle members such as decorative films and transfer films, furniture doors and surfaces, floor coverings, doors, window frames, windows, walls , Door knobs, roofs, entrance floors, tiles, bridges, tarpaulins, bottom film, light control films, etc.
  • Optical components such as lenses, polarizers, wavelength conversion elements, and sensors, buttons and surface members of home appliances, energy-related members such as solar cells, wind power generation, fuel cells, and piezoelectric films.
  • Semiconductor materials such as buffer coats, nonconductive films, cover films, mold release films, resists, cards, inkjet paper, thermal paper, marking films, design films, signs, advertising materials, decorative materials, sign signs, supplies for printers It can be applied to recording and graphic members such as copier rolls and heat sealers, kitchen counters, sinks, vanities, kitchen and sanitary members such as tub walls and ceilings, and various hard coating materials used indoors and out.
  • Synthesis example 1 In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 1.2 g (1.9 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 3- Add 26.0 g (0.1 mol) of glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), stir, add 6.4 g of a 0.05% aqueous hydrochloric acid solution to the dropping funnel (water content: hydrolysis) 1 mole of the sex group was added and added with stirring at room temperature.
  • Synthesis example 2 16.5 g (0.027 mol) of KBM 9659, 1.0 g (0.004 mol) of KBM-403 and 5.9 g of PGME are added to a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, and the mixture is stirred and dropped. Then, 4.7 g of a 0.05% aqueous hydrochloric acid solution was added thereto, and the mixture was added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling to obtain a target siloxane condensate (siloxane resin solution A2). The epoxy equivalent of the obtained reactant was 3890.
  • Synthesis example 3 Add 21.7 g (0.035 mol) of KBM 9659 and 2.5 g (0.1 mol) of KBM-403 into a reaction vessel equipped with a stirrer, dropping funnel, and thermometer, and stir, and add 0.05% hydrochloric acid to the dropping funnel. 11.6 g of an aqueous solution was charged and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 17.6 g of PGME was added to obtain a target siloxane condensate (siloxane resin solution A3). The epoxy equivalent of the obtained reactant was 422, and the molecular weight was 43,600.
  • Synthesis example 4 30.0 g (0.12 mol) of 3-methacryloxypropyltrimethoxysilane (XIAMETER OFS 6030: manufactured by Toray Dow Corning) in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 0.05% in the dropping funnel 9.3 g of a hydrochloric acid aqueous solution was charged and added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, and then cooled and 5.8 g of PGME was added to obtain a target siloxane condensate (siloxane resin solution A4, molecular weight 1000).
  • siloxane resin solutions A1 to A4 obtained in the above synthesis example, the polymerization initiator and the solvent were blended in proportions (parts by weight) shown in Table 1 to obtain siloxane-based curable resin compositions (hard coating liquids) H1 to H5.
  • CPI-100 (San Apro) used as a curing catalyst is a photoacid generator
  • WPBG-266 (Wako Pure Chemical Industries, Ltd.) is a photo base generator
  • SI-80 Sanshin Chemical Industries
  • Irg 184 (BASF) is a radical photoinitiator
  • the solvent is PGME.
  • hard coating film Siloxane-based curable resin composition (hard coating liquid) H-1, H-2, H-3, H-5 compounded in the ratio of Table 1 above, each with PET substrate
  • the solution was applied by spin coating to a thickness of 100 ⁇ m, a length of 10 cm, and a width of 10 cm, dried at 80 ° C. for 6 minutes, and then cooled at room temperature for 5 minutes. Then, it formed into a film by 400 mJ / cm ⁇ 2 > accumulated exposure amount (365 nm conversion) using a high-pressure mercury lamp of 2 kW / cm ⁇ 2> in oxygen atmosphere.
  • the siloxane-based curable resin composition (hard coating solution) H-4 of Example 4 was applied to a PET substrate (thickness 100 ⁇ m, length 10 cm, width 10 cm) by spin coating, and was applied at 80 ° C. for 6 minutes. After drying, the film was further heated at 100 ° C. for 30 minutes to form a film.
  • Synthesis example 5 In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 1.2 g (1.9 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 3- Add 26.0 g (0.1 mol) of glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), stir, add 6.4 g of a 0.05% aqueous hydrochloric acid solution to the dropping funnel (water content: hydrolysis) 1 mole of the sex group was added and added with stirring at room temperature.
  • aqueous hydrochloric acid solution water content: hydrolysis
  • Synthesis example 6 In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 1.1 g (1.8 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 2- 25.0 g (0.1 mol) of (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-303) is added and stirred, and 5.9 g of 0.05% aqueous hydrochloric acid solution is added to the dropping funnel.
  • 1,3,5-tris (trimethoxysilylpropyl) isocyanurate Shin-Etsu Chemical Co., Ltd .: KBM 9659
  • siloxane-based curable resin composition was prepared by blending the siloxane resin solutions A5 to A6, the epoxy resin E1, the photocationic polymerization initiator, the surface conditioner, and the solvent obtained in the above synthesis example in the proportions (parts by weight) shown in Table 3. Hard coating solutions) H6 to H16 were obtained.
  • siloxane-based curable resin compositions H6 to H16 obtained in Examples 5 to 14 and Comparative Example 2 were spin-coated on a PET substrate (thickness 100 ⁇ m, length 10 cm, width 10 cm) The solution was applied, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes. Thereafter, a film test piece with a film thickness of 10 ⁇ m was obtained by forming a film with a 400 mJ / cm 2 cumulative exposure dose (converted to 365 nm) using a 2 kW / cm 2 high pressure mercury lamp under an oxygen atmosphere.
  • the film test pieces were measured using a UV-VIS SPECTROPHOTOMETER UV-3600Plus (manufactured by Shimadzu Corporation) with the PET substrate as a blank.
  • Synthesis example 7 In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 2.5 g (4.0 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 3- Add 26.0 g (0.1 mol) of glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), stir, add 6.7 g of a 0.05% aqueous hydrochloric acid solution to the dropping funnel (water content: hydrolysis) 1 mole of the sex group was added and added with stirring at room temperature.
  • aqueous hydrochloric acid solution water content: hydrolysis
  • Synthesis example 8 In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 2.5 g (4.0 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 2- 26.0 g (0.1 mol) of (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-303) is added and stirred, and 6.7 g of a 0.05% aqueous hydrochloric acid solution is added to the dropping funnel.
  • 1,3,5-tris (trimethoxysilylpropyl) isocyanurate Shin-Etsu Chemical Co., Ltd .: KBM 9659
  • Synthesis example 9 30.0 g (0.12 mol) of 3-methacryloxypropyltrimethoxysilane (XIAMETER OFS 6030: manufactured by Toray Dow Corning) in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 0.05% in the dropping funnel 9.3 g of a hydrochloric acid aqueous solution was charged and added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, and then cooled and 5.8 g of PGME was added to obtain a target siloxane condensate (siloxane resin solution A9).
  • XIAMETER OFS 6030 manufactured by Toray Dow Corning
  • WPI-116 manufactured by Wako Pure Chemical Industries, Ltd.
  • WPBG-266 manufactured by Wako Pure Chemical Industries, Ltd.
  • SI-80 manufactured by Sanshin Chemical Industries, Ltd.
  • Is a cationic polymerization initiator Irg 184 (manufactured by IGM) is a radical photopolymerization initiator, and the solvent is PGME.
  • resin agent 30 parts by weight of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A), 70 parts by weight of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co .: UA-306H) 3 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Japan Ltd .; Irgaqure 819) as a polymerization initiator, and 333 parts by weight of propylene glycol monomethyl ether as a solvent, I got P-1).
  • dimethylol-tricyclodecane diacrylate manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A
  • Example 15 The hard coating solution H-17 obtained in Preparation Example 1 is applied to a PET substrate (thickness 100 ⁇ m, length 10 cm, width 10 cm) by spin coating, dried at 80 ° C. for 6 minutes, and then at room temperature 5 It cooled for a minute. Then, using a 2 kW / cm 2 high-pressure mercury lamp in an oxygen atmosphere, a film is formed at 1000 mJ / cm 2 cumulative exposure dose (365 nm equivalent), and a hard coating (HC) film is formed on the PET substrate surface A coated PET laminate was obtained.
  • Examples 16, 17 and Comparative Example 3 An HC coated PET laminate was obtained in the same manner as in Example 15 except that the hard coating solution had the composition shown in Table 6, except that a hard coating was formed on the surface of the PET substrate.
  • Example 18 The hard coating solution H-20 obtained in Preparation Example 4 is applied to a PET substrate (thickness 100 ⁇ m, length 10 cm, width 10 cm) by spin coating, dried at 80 ° C. for 6 minutes, and then 100 A film was formed by heating at 30 ° C. for 30 minutes, and a HC coated PET laminate obtained by forming a hard coating film on the surface of the PET substrate was obtained.
  • Example 19 The coating solution of the resin composition (P-1) is applied to a PC substrate (3 mm thick, 10 cm long, 10 cm wide) by spin coating, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes did. Then, the resin layer was formed into a film by 100 mJ / cm ⁇ 2 > accumulated exposure amount (365 nm conversion) using a 2 kW / cm ⁇ 2> high pressure mercury lamp in oxygen atmosphere. Next, the hard coating solution H-17 obtained in Preparation Example 1 was applied to the resin layer by spin coating, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes.
  • Example 20 A solution of a surface treatment agent (S-1) was applied to an aluminum plate by spin coating, the surface of the aluminum plate was treated, and dried at 100 ° C. for 5 minutes. Next, the hard coating solution H-17 obtained in Preparation Example 1 was applied to the resin layer by spin coating, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes. Then, an oxygen atmosphere, using a high-pressure mercury lamp of 2 kW / cm 2, was deposited at 1000 mJ / cm 2 cumulative exposure amount (365 nm equivalent), by forming a hard coating film on an aluminum substrate surface-treated HC coating An attached aluminum laminate was obtained.
  • S-1 surface treatment agent
  • Example 21 The hard coating solution H-17 obtained in Preparation Example 1 is applied to an aluminum substrate (thickness 500 ⁇ m, length 10 cm, width 10 cm) by spin coating, dried at 80 ° C. for 6 minutes, and then at room temperature 5 It cooled for a minute. After that, using a 2 kW / cm 2 high-pressure mercury lamp in an oxygen atmosphere, a film is formed at 1000 mJ / cm 2 cumulative exposure dose (converted to 365 nm), and a hard coating film is formed on the aluminum substrate. I got a body.
  • the siloxane-based curable resin composition of the present invention can be widely used as a paint, a hard coat material, etc. excellent in abrasion resistance and transparency.
  • the composition and the hard coating solution can be widely used as various hard coating materials such as, for example, electronic members such as displays and casings, interiors of automobiles, home electric appliances members, and construction members.
  • the siloxane-based curable resin composition of the present invention as a hard coating solution, atmospheric curing in a short time is possible, and the substrate surface is hard-coated through another resin layer, if necessary.
  • the laminated body formed by forming the hard siloxane resin layer as a film can be provided.
  • This laminate includes, for example, electronic parts such as displays and casings, vehicle members such as interiors and windows, optical members such as furniture and building members lenses, surface members of home appliances, energy related members such as solar cells, buffers
  • the present invention can be applied to various hard coating materials used indoors and outdoors, such as semiconductor members such as coats, graphic members such as recording members and design films, and sanitary members such as kitchen counters and vanities.

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Abstract

L'invention concerne une composition de résine durcissable qui peut rapidement durcir dans l'air et qui est utile pour un matériau de revêtement dur ayant une excellente résistance aux rayures, une excellente transparence, etc. La composition de résine durcissable de type siloxane comprend le produit d'hydrolyse-condensation partielle du composant suivant (A) et du composant (B) et est caractérisée en ce que le produit d'hydrolyse-condensation partielle a un poids équivalent époxy (g/éq) de 200 à 4 000 : composant (A) : un alkoxysilane portant une structure en anneau d'isocyanurate ou un produit d'hydrolyse-condensation partielle de celui-ci; et un composant (B) : un alcoxysilane portant un groupe époxy ou un groupe oxétane ou un produit d'hydrolyse-condensation partielle de celui-ci.
PCT/JP2018/033187 2017-12-22 2018-09-07 Composition de résine durcissable de type siloxane et liquide de revêtement dur Ceased WO2019123731A1 (fr)

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JP2017-246132 2017-12-22
JP2017246132A JP2019112519A (ja) 2017-12-22 2017-12-22 シロキサン系硬化性樹脂組成物及びハードコーティング液
JP2018-035070 2018-02-28
JP2018035070A JP7320922B2 (ja) 2018-02-28 2018-02-28 シロキサン系硬化性樹脂組成物から成るハードコーティング液を用いた積層体

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CN112608691A (zh) * 2019-10-04 2021-04-06 琳得科株式会社 书写感改善片
WO2024116877A1 (fr) * 2022-11-30 2024-06-06 株式会社スリーボンド Composition de résine photodurcissable

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JP7424788B2 (ja) * 2019-10-04 2024-01-30 日鉄ケミカル＆マテリアル株式会社 シロキサン樹脂を含む硬化性樹脂組成物、及びその硬化膜、シロキサン樹脂の製造方法

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