WO2011065155A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2011065155A1
WO2011065155A1 PCT/JP2010/068331 JP2010068331W WO2011065155A1 WO 2011065155 A1 WO2011065155 A1 WO 2011065155A1 JP 2010068331 W JP2010068331 W JP 2010068331W WO 2011065155 A1 WO2011065155 A1 WO 2011065155A1
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WIPO (PCT)
Prior art keywords
structural unit
resin composition
curable resin
formula
fluorine
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PCT/JP2010/068331
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English (en)
Japanese (ja)
Inventor
義人 田中
崇 金村
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ダイキン工業株式会社
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Priority to JP2011543173A priority Critical patent/JP5494671B2/ja
Publication of WO2011065155A1 publication Critical patent/WO2011065155A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08K5/54—Silicon-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a curable resin composition containing a fluorine-containing polymer that is cured by a hydrosilylation reaction.
  • Patent Document 1 a composition relating to a curable fluorine-containing polymer having an ethylenic carbon-carbon double bond at a terminal
  • Patent Document 2 proposes that a fluorine-containing polymer having an ethylenic carbon-carbon double bond is cured by a hydrosilylation reaction.
  • the crosslinking reaction disclosed in Patent Document 1 is a photocuring reaction, and a curing system based on a hydrosilylation reaction is not disclosed.
  • the fluorine-containing polymer described in Patent Document 2 is a copolymer of a fluorinated ethylenic monomer and a non-fluorinated ethylenic monomer, and is a structural unit that provides an ethylenic carbon-carbon double bond Is a polymer derived from a non-fluorinated ethylenic monomer.
  • the structural unit giving an ethylenic carbon-carbon double bond is a non-fluorinated ethylenic structural unit, the fluorine content of the fluoropolymer cannot be increased, and optical properties such as light transmittance and refractive index are not obtained. There is room for further improvement in terms of characteristics, heat resistance at high temperatures, and light resistance.
  • An object of the present invention is to provide a curable resin composition that can increase the fluorine content and can easily cause a hydrosilylation reaction.
  • Another object of the present invention is to provide a curable resin composition that can be easily cured without containing an organic solvent that does not participate in the hydrosilylation reaction.
  • the present invention (A) Formula (I): (Wherein X 1 and X 2 are the same or different and are a fluorine atom or a hydrogen atom; X 3 is a fluorine atom, a hydrogen atom, a chlorine atom, a methyl group, or a trifluoromethyl group; are X 4 and X 5 the same?
  • a fluorine-containing polymer comprising the structural unit (I) represented by The present invention relates to a curable resin composition containing (B) a hydrosilylation crosslinking agent and (C) a hydrosilylation catalyst.
  • the present invention also relates to a cured product obtained by curing the curable resin composition of the present invention.
  • the resulting cured product has optical properties such as refractive index and transparency in the ultraviolet or near infrared region, light resistance, and weather resistance. Heat resistance, water absorption, water and oil repellency, and chemical resistance can be improved.
  • the crosslinking reaction of the curable resin composition of the present invention is not a reaction in which a desorbing component such as water or salt is generated but an addition reaction, so that a step of removing a by-product is not required.
  • a composition having a predetermined viscosity can be prepared without using a solvent that does not participate in the crosslinking reaction, and crosslinking (curing) can be easily performed. Moreover, the process of removing a solvent from the hardened
  • the curable resin composition of the present invention includes (A) a fluorine-containing polymer containing the structural unit (I) represented by the formula (I), (B) a hydrosilylation crosslinking agent, and (C) a hydrosilylation catalyst. .
  • One of the characteristics of the composition of the present invention is that the fluoropolymer (A) has an ethylenic carbon-carbon double bond.
  • the fluorine-containing structural unit (I) having a chain is included.
  • Such fluorine-containing structural unit (I) is represented by the formula (I): (Wherein X 1 and X 2 are the same or different and are a fluorine atom or a hydrogen atom; X 3 is a fluorine atom, a hydrogen atom, a chlorine atom, a methyl group, or a trifluoromethyl group; are X 4 and X 5 the same?
  • Z include, for example, alkenyl groups such as vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and octenyl group; alkenyl groups such as vinylphenyl group and isopropenylphenyl group Aryl group; vinylphenylmethyl group, formula: An alkenyl group-containing aralkyl group such as a group represented by the formula:
  • Y corresponds to a necessary linking group for the reaction of introducing a carbon-carbon double bond into a polymer chain, and when introducing a carbon-carbon double bond via esterification, urethanization, or etherification —C ( ⁇ O) O—, or —O (C ⁇ O) —, —C ( ⁇ O) N (—H) —, or —N (—H) C ( ⁇ O) —, —O respectively.
  • —C ( ⁇ O) O—, —O (C ⁇ O) — or —O— is particularly preferable from the viewpoint of good heat resistance, weather resistance, and light resistance.
  • —C ( ⁇ O) N (—H) — is preferable because of easy synthesis.
  • the fluorine-containing structural unit (I) is preferably the following structural unit from the viewpoint of good optical characteristics such as transparency, light resistance, weather resistance, and heat resistance.
  • M is an integer from 0 to 5)
  • the fluoropolymer (A) may contain other structural units in addition to the structural unit (I).
  • the formula (1) -(A)-(M)-(N)- (In the formula, A is a structural unit represented by the formula (I); M is a structural unit derived from a fluorine-containing ethylenic monomer having a functional group; N is a monomer unit that gives structural units A and M; A structural unit derived from a polymerizable monomer) and comprising 1 to 100 mol% of structural unit A, 0 to 99 mol% of structural unit M and 0 to 80 mol% of structural unit N) Examples thereof include the fluorine-containing polymer represented.
  • the optical properties such as transparency, light resistance, weather resistance, and heat resistance are favorable.
  • the copolymerization ratio is preferably such that structural unit A / structural unit M / structural unit N is 1 to 100/99 to 0/80 to 0 (mole% ratio), more preferably 5 to 50/95 to 50/50 to 0. (Mole% ratio).
  • the number average molecular weight of the fluorinated polymer (A) is not particularly limited, but as described later, from the viewpoint of solubility in the hydrosilylation crosslinking agent (B) and the solvent (D), it is preferably from 5,000 to 1,000,000. It is preferably 7,000 to 500,000.
  • hydrosilylation cross-linking agent (B) Hydrosilylation cross-linking agent
  • the hydrosilylation reaction is an addition reaction between an ethylenic carbon-carbon double bond and a hydrogen atom directly bonded to a silicon atom. Therefore, the hydrosilylation cross-linking agent (B) in the present invention is used. Is a silicon compound having in the molecule two or more groups in which hydrogen atoms are directly bonded to silicon atoms.
  • hydrosilylation crosslinking agent (B) examples include International Publication No. 2008/153002, International Publication No. 2008/044765, International Patent Application PCT / JP2007 / 074066, and International Patent Application PCT / JP2008 / 060555. Those described in the specification can be used.
  • B1, B2, and B3 described in International Publication No. 2008/044765 pamphlet can be used as they are.
  • hydrosilylation crosslinking agent (B) is a hydrogen that can dissolve or disperse fluoropolymer (A) from the new viewpoint of affinity with fluoropolymer (A), particularly solubility and dispersibility.
  • Liquid siloxane compound (B4) having two or more groups in which atoms are directly bonded to silicon atoms hereinafter sometimes referred to as “soluble hydrosilylation crosslinking agent (B4)”
  • Siloxane-based compound (B5) hereinafter referred to as “insoluble hydrosilylation crosslinking agent (B5) having two or more groups in which hydrogen atoms are directly bonded to silicon atoms” in a liquid or solid state in which the compound (A) is not dissolved or dispersed. ) ").
  • Soluble hydrosilylation crosslinking agent A liquid siloxane compound having two or more groups in which hydrogen atoms are directly bonded to silicon atoms, and crosslinks (cures) the fluoropolymer (A) by a hydrosilylation reaction. It is a siloxane-based compound that has the ability to dissolve or disperse the fluoropolymer (A).
  • the solventless curable resin composition is useful even in cases where volatile components are not allowed due to molding processing conditions. For example, it is advantageous in applications such as filling and sealing in an airtight container.
  • soluble hydrosilylation crosslinking agent (B4) for example, B1 and B2 described in International Publication No. 2008/044765 pamphlet can be used as they are.
  • Non-soluble hydrosilylation cross-linking agent A siloxane compound other than the soluble hydrosilylation cross-linking agent (B4), which is a liquid or solid that does not dissolve or disperse the fluoropolymer (A) and has hydrogen atoms.
  • this non-soluble hydrosilylation crosslinking agent (B5) When using this non-soluble hydrosilylation crosslinking agent (B5), use a solvent (D) that dissolves or disperses the fluoropolymer (A), or use a soluble hydrosilylation crosslinking agent (B4) in combination. It is required to do.
  • non-soluble hydrosilylation crosslinking agent (B5) for example, B3 described in International Publication No. 2008/044765 can be used as it is.
  • the non-soluble hydrosilylation crosslinking agent (B5) specifically, an average unit formula: ⁇ H (CH 3 ) 2 SiO 1/2 ⁇ d (SiO 4/2 ) f ′
  • the blending amount of the hydrosilylation crosslinking agent (B) varies depending on the type of the fluoropolymer, the type of the hydrosilylation crosslinking agent, the presence or absence of a solvent, the type, etc. From the point of function as a crosslinking agent, the fluoropolymer (A) 5 parts by mass or more, further 10 parts by mass or more, particularly 20 parts by mass or more, and 90 parts by mass or less, further 70 parts by mass or less, particularly 50 parts by mass or less with respect to 100 parts by mass. preferable.
  • the fluoropolymer (A) also serves as a solvent (in the case of the soluble hydrosilylation crosslinking agent (B4)), 30 parts by mass or more with respect to 100 parts by mass of the fluoropolymer (A). Furthermore, it is 50 parts by mass or more, particularly 70 parts by mass or more, and 500 parts by mass or less, more preferably 300 parts by mass or less, and particularly preferably 200 parts by mass or less.
  • (C) Hydrosilylation catalyst A compound that catalyzes a known hydrosilylation reaction can be used. For example, those described in International Publication No. 2008/153002, International Publication No. 2008/044765, International Patent Application PCT / JP2007 / 074066, International Patent Application PCT / JP2008 / 060555, etc. Can be used.
  • the hydrosilylation catalyst (C) is a catalyst for promoting the hydrosilylation reaction of the composition of the present invention.
  • catalysts include platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, ruthenium-based catalysts, and iridium-based catalysts, and platinum-based catalysts are preferred because they are relatively easily available.
  • platinum-based catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum carbonyl complex, platinum olefin complex, and platinum alkenylsiloxane complex.
  • platinum complexes include platinum carbonylcyclovinylmethylsiloxane complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, etc. It can be obtained as a reagent having a platinum concentration of 1 to 5%, such as a methyl cyclic siloxane solution, a vinyl polydimethylsiloxane solution having both ends of a platinum-divinyltetramethyldisiloxane complex, and a cyclic methylvinylsiloxane solution of a platinum-cyclovinylmethylsiloxane complex.
  • the content of the hydrosilylation reaction catalyst (C) is a catalyst amount that accelerates the curing of the composition of the present invention.
  • the content of the catalyst metal in the composition of the present invention is preferably in an amount in the range of 0.1 to 1,000 ppm by mass, and particularly preferably in the range of 1 to 500 ppm. If the content of the component (C) is less than the lower limit of the above range, curing of the resulting composition may not be sufficiently promoted. This is because problems such as coloring may occur in the cured product.
  • the solvent (D) in the present invention mainly has a role of dissolving or dispersing the fluoropolymer (A).
  • the solvent used only to dissolve or disperse the fluoropolymer (A) may cause a problem that the organic solvent remains in the cured product when the removal is insufficient, or the heat resistance is affected by the remaining organic solvent.
  • problems such as deterioration of mechanical properties, mechanical strength, and cloudiness, or voids may be generated due to volatilization of the solvent, it is desirable to remove the solvent as completely as possible. Therefore, it is desirable not to use as much as possible from the viewpoint of environment and cost, including energy for that purpose.
  • a solvent (D) that can dissolve or disperse the fluoropolymer (A) is used as a non-silicon-based solvent that participates in the hydrosilylation crosslinking reaction. They are classified into a reactive solvent (D1) and a solvent (D2) that does not participate in the hydrosilylation crosslinking reaction.
  • Non-silicon reactive solvent involved in hydrosilylation crosslinking reaction The soluble hydrosilylation crosslinking agent (B4) is also a compound that dissolves and disperses the fluoropolymer (A) and participates in the hydrosilylation crosslinking reaction. Although it is a siloxane compound, it is not a solvent (D1).
  • “involved in the hydrosilylation crosslinking reaction” means any reaction involved in the hydrosilylation reaction, which is an addition reaction between an ethylenic carbon-carbon double bond and a hydrogen atom directly bonded to a silicon atom. It has a group (ethylenic carbon-carbon double bond or silicon atom-bonded hydrogen atom-containing group), and as a result, is incorporated into the reaction product of the hydrosilylation crosslinking reaction. Moreover, it is preferable to have a some reactive group from a viewpoint that there exists crosslinking
  • polyvalent allyl compounds such as ethylene glycol diallyl, diethylene glycol diallyl, triethylene glycol diallyl, 1,4-cyclohexanedimethanol diallyl, triallyl isocyanurate (TAIC); ethylene glycol divinyl ether, diethylene glycol Divinyl ether, triethylene glycol divinyl ether, bisphenol A bis (vinyloxyethylene) ether, bis (vinyloxyethylene) ether, hydroquinone bis (vinyloxyethylene) ether, 1,4-cyclohexanedimethanol divinyl ether, Polyvalent vinyl ether compounds such as ethylene glycol diacrylate (EDA), diethylene glycol diacrylate (DiEDA), triethylene glycol diacrylate (TriEDA), 1,4-butanediol diacrylate (1,4-BuDA), 1,3 -Butanediol diacrylate (1,3-BuDA), 2,2-bis [4- (2-hydroxy-3-acryloxypropoxy) phenyl
  • TAIC EDMA
  • EDA EDA
  • TMPT TMPA
  • TMPA TMPA
  • the non-silicon-based reactive solvent (D1) may be used alone as the reactive solvent for the fluoropolymer (A), or the soluble hydrosilylation crosslinking agent (B4) or non-reactive which also functions as a solvent. May be used in combination with the solvent (D2).
  • the compounding amount of the non-silicon-based reactive solvent (D1) varies depending on the type of the fluoropolymer, the type of the solvent (D1), the presence or absence of other solvents, the type, etc., but from the point of function as hydrosilylation reactivity Is 5 parts by mass or more, further 10 parts by mass or more, particularly 20 parts by mass or more, and 90 parts by mass or less, further 70 parts by mass or less, relative to 100 parts by mass of the fluoropolymer (A). In particular, 50 parts by mass or less is preferable.
  • the role as a solvent of a fluoropolymer (A) when the role as a solvent of a fluoropolymer (A) can also be used, it is 30 mass parts or more with respect to 100 mass parts of fluoropolymer (A), Furthermore, 50 mass parts or more, Especially 70 mass parts or more. Moreover, 500 mass parts or less, Furthermore, 300 mass parts or less, Especially 200 mass parts or less are preferable.
  • (D2) Solvent that does not participate in hydrosilylation crosslinking reaction This solvent (D2) is used in the case where the soluble hydrosilylation crosslinking agent (B4) and the non-silicon reactive solvent (D1) are not blended, or only by them. What is necessary is just to use when the solubility and dispersibility of a unification
  • aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; Methyl, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl Such as acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl
  • fluorine-based solvent for example, CH 3 CCl 2 F (HCFC-141b), CF 3 CF 2 CHCl 2 / CClF 2 CF 2 CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2- Butyltetrahydrofuran), methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, etc.
  • fluorinated solvents may be used alone, or may be fluorinated solvents, or a mixed solvent of one or more of non-fluorinated and fluorinated solvents.
  • the curable resin composition of the present invention can be a so-called solvent-free curable resin composition that does not use the solvent (D2) that does not participate in the hydrosilylation crosslinking reaction (however, the solvent is not non-volatile).
  • the case where only the silicon-based reactive solvent (D1) is used is also referred to as a solventless type).
  • the solvent-free type in this way, it is not necessary to remove the solvent (D2), the molding process and the like can be simplified, and the problem that the solvent (D2) remains in the cured product does not occur.
  • the solventless curable resin composition is useful even in cases where volatile components are not allowed due to molding processing conditions. For example, it is used for filling and sealing in an airtight container.
  • the curable resin composition of the present invention varies depending on the application, for example, for applications such as sealing, if the viscosity at 30 ° C. is too low, there is a lot of liquid dripping, and on the contrary, the handleability is lowered. It is preferably 1 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more from the viewpoint of good thin film formability, and further preferably 10 mPa ⁇ s or more from the viewpoint of small cure shrinkage during curing.
  • mPa ⁇ s or less is preferable, and from the viewpoint that the curable composition spreads over the details during molding, 5000 mPa ⁇ s or less is more preferable, and when a thin film is formed. From the viewpoint of good leveling (surface smoothness), 2000 mPa ⁇ s or less is more preferable.
  • Form 1 (solvent-free type)
  • A Fluoropolymer: In the formula (1), the structural unit A is the formula (Ia), and the structural unit M is Fluoropolymer (B) hydrosilylation crosslinking agent having a weight average molecular weight of 5,000 to 20,000 Soluble hydrosilylation crosslinking agent (B4) (C) Hydrosilylation catalyst Platinum catalyst (D) Solvent None (Preparation method) After (A) is uniformly dissolved in (B4), (C) is added to obtain a curable composition.
  • Form 2 (solvent-free type)
  • A Fluoropolymer: In the formula (1), the structural unit A is the formula (Ia), and the structural unit M is A fluorine-containing polymer having a weight average molecular weight of 5,000 to 20,000
  • B hydrosilylation crosslinking agent soluble hydrosilylation crosslinking agent (B4) and non-soluble hydrosilylation crosslinking agent (B5)
  • B5 Hydrosilylation catalyst Platinum catalyst
  • D Solvent None (Preparation method) (B) is added after (A) is uniformly dissolved in (B4). Thereafter, (C) is added to obtain a curable composition.
  • Form 3 (solvent-free type)
  • A Fluoropolymer: In the formula (1), the structural unit A is the formula (Ia), and the structural unit M is A fluorine-containing polymer having a weight average molecular weight of 5,000 to 20,000
  • B hydrosilylation crosslinking agent soluble hydrosilylation crosslinking agent (B4) and / or insoluble hydrosilylation crosslinking agent (B5)
  • C Hydrosilylation catalyst Platinum catalyst
  • D solvent Non-silicon reactive solvent (D1) (Preparation method) After (A) is uniformly dissolved in (D1), (B4) and / or (B5) is added to make it uniform. Thereafter, (C) is added to obtain a curable composition.
  • Form 4 (solvent type)
  • A Fluoropolymer: In the formula (1), the structural unit A is the formula (Ia), and the structural unit M is Fluoropolymer (B) hydrosilylation crosslinking agent having a weight average molecular weight of 50,000 to 200,000 Soluble hydrosilylation crosslinking agent (B4) and / or non-solubility hydrosilylation crosslinking agent (B5)
  • B hydrosilylation crosslinking agent having a weight average molecular weight of 50,000 to 200,000 Soluble hydrosilylation crosslinking agent (B4) and / or non-solubility hydrosilylation crosslinking agent (B5)
  • C Hydrosilylation catalyst Platinum catalyst
  • D solvent Non-reactive solvent (D2) (Preparation method) (A) is uniformly dissolved in (D2), and after (B4) and / or (B5) is added, it is made uniform. Thereafter, (C) is added to obtain a curable composition.
  • Form 5 (solvent type)
  • A Fluoropolymer: In the formula (1), the structural unit A is the formula (Ia), and the structural unit M is Fluoropolymer (B) hydrosilylation crosslinking agent having a weight average molecular weight of 50,000 to 200,000 Soluble hydrosilylation crosslinking agent (B4) and / or non-solubility hydrosilylation crosslinking agent (B5)
  • B hydrosilylation crosslinking agent having a weight average molecular weight of 50,000 to 200,000 Soluble hydrosilylation crosslinking agent (B4) and / or non-solubility hydrosilylation crosslinking agent (B5)
  • C Hydrosilylation catalyst Platinum catalyst
  • D solvent Non-reactive solvent (D2) and non-silicon-based reactive solvent (D1)
  • Preparation method (A) is uniformly dissolved in the mixed solution of (D2) and (D1), and then (B4) and / or (B5) is added, and the mixture is made uniform. Thereafter, (
  • the curable resin composition of the present invention optionally includes, for example, reaction inhibitors, pigments, dispersants, thickeners, preservatives, ultraviolet absorbers, antifoaming agents, leveling agents, etc. May be.
  • reaction inhibitor examples include 1-ethynyl-1-cyclohexanol, 2-ethynylisopropanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl.
  • Acetylenic alcohols such as -3-butyn-2-ol; alkenyl siloxanes such as 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane; malate compounds such as diallyl fumarate, dimethyl fumarate and diethyl fumarate;
  • Other examples include triallyl cyanurate and triazole.
  • the effect of being able to make the obtained composition one component and the pot life (pot life) of the resulting composition to be sufficiently long is exhibited.
  • the content of the reaction inhibitor is not particularly limited, but is preferably such an amount that it is 10 to 50,000 ppm (mass basis) in the composition of the present invention.
  • the curable resin composition of the present invention is cured by hydrosilylation crosslinking, and the resulting cured product can be used in various forms for various applications.
  • a cured film can be formed and used for various purposes.
  • a method of forming the film a known method suitable for the application can be employed. For example, when it is necessary to control the film thickness, roll coating, gravure coating, micro gravure coating, flow coating, bar coating, spray coating, die coating, spin coating, dip coating, etc. are used. it can.
  • the curable resin composition of the present invention may be used for film formation, but is particularly useful as a molding material for various molded products.
  • As the molding method extrusion molding, injection molding, compression molding, blow molding, transfer molding, stereolithography, nanoimprinting, vacuum molding and the like can be adopted.
  • Examples of the use of the curable resin composition of the present invention include a sealing member, an optical material, an optoelectronic imaging tube, various sensors, and an antireflection material.
  • sealing member examples include packages (encapsulation) and mounting of light-emitting elements such as light-emitting diodes (LEDs), EL elements, and nonlinear optical elements, and optical functional elements such as light-receiving elements such as CCD, CMOS, and PD. Can be illustrated. Moreover, sealing materials (or fillers) for optical members such as lenses for deep ultraviolet microscopes are also included. Sealed light elements are used in various places, but non-limiting examples include light emission from high-mount stop lamps, meter panels, mobile phone backlights, and light sources for remote control devices for various electrical products. Elements: Camera autofocus, CD / DVD optical pickup light receiving element, and the like.
  • the optical material contains fluorine in particular, it becomes an optical material with a low refractive index.
  • it is useful as an optical transmission medium.
  • cladding material of plastic clad optical fiber whose core material is quartz or optical glass, cladding material of all plastic optical fiber whose core material is plastic, anti-reflection coating material, lens material, optical waveguide material, prism material, optical window
  • lens material optical waveguide material
  • prism material optical window
  • optical materials such as materials, optical storage disk materials, nonlinear optical elements, hologram materials, photolithographic materials, and light emitting element sealing materials. It can also be used as a material for optical devices.
  • optical devices such as optical waveguides, OADMs, optical switches, optical filters, optical connectors, multiplexers / demultiplexers, and other optical devices are known and useful for forming these devices. Material. Furthermore, various functional compounds (non-linear optical materials, fluorescent light-emitting functional dyes, photorefractive materials, etc.) are contained and used as functional elements for optical devices such as modulators, wavelength conversion elements, and optical amplifiers. Is suitable.
  • the sealing member material for electronic semiconductors, a water and moisture resistant adhesive, and an adhesive for optical components and elements.
  • IR analyzer Fourier transform infrared spectrophotometer 1760X manufactured by PERKIN ELMER Conditions: Measure at room temperature.
  • Hydroxyl value (mgKOH / g) The hydroxyl value is determined according to a conventional method by an acetylation method using acetic anhydride.
  • Fluorine content (% by mass) By burning 10 mg of sample by the oxygen flask combustion method, absorbing the decomposition gas in 20 ml of deionized water, and measuring the fluorine ion concentration in the absorption liquid by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion) Ask.
  • Viscosity (mPa ⁇ s) Using a cone-plate viscometer CV-1E manufactured by Tokai Yagami Co., Ltd., the viscosity at 25 ° C. is measured using CP-100 cone under the condition of 100 rpm, and a stable value is adopted for 60 seconds.
  • Refractive index (n D ) Measurement is performed using an Abbe refractometer manufactured by Atago Optical Instruments Co., Ltd. at 25 ° C. using sodium D line (589 nm) as a light source.
  • Light transmittance (%) A value obtained by measuring a spectral transmittance curve of a sample (cured film) having a thickness of about 100 ⁇ m at a wavelength of 300 to 800 nm using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.) is adopted.
  • a solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, separated and vacuum dried to obtain 13.2 g of a colorless and transparent polymer.
  • This polymer was analyzed by 19 F-NMR, 1 H-NMR analysis, and IR analysis. As a result, it was a fluorine-containing polymer comprising only the structural unit of the fluorine-containing allyl ether and having a hydroxyl group at the end of the side chain.
  • the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 86,000, and the weight average molecular weight was 108,000.
  • the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone.
  • Synthesis Example 2 Synthesis of fluorinated allyl ether homopolymer having OH group
  • a stirrer and a thermometer 100.2 g of AEH1 and 42.5 g of HCFC-225, perbutyl PV (peroxide system manufactured by NOF Corporation) as a polymerization initiator 3.36 g of a polymerization initiator
  • stirring was performed at 65 ° C. for 12 hours under a nitrogen stream to obtain a highly viscous solution.
  • the obtained polymer solution was poured into perfluorohexane, separated and vacuum dried to obtain 61.8 g of a colorless and transparent polymer.
  • This polymer was analyzed by 19 F-NMR, 1 H-NMR analysis, and IR analysis. As a result, it was a fluorine-containing polymer comprising only the structural unit of the fluorine-containing allyl ether and having a hydroxyl group at the end of the side chain.
  • the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 11000, and the weight average molecular weight was 15700.
  • the MIBK solution was put in a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water. The organic layer was separated and dried over anhydrous magnesium sulfate.
  • reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone.
  • the polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of 3 times to obtain 3.4 g of a viscous polymer.
  • This polymer was analyzed by 19 F-NMR, 1 H-NMR analysis, and IR analysis. As a result, it was found that the fluorine-containing copolymer comprising the hydroxyl group-containing fluorine-containing allyl ether and the fluorine-containing allyl ether having a methyl ester structure. It was a polymer.
  • the composition ratio was determined to be 42:58 (molar ratio) by NMR.
  • the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 7200, and the weight average molecular weight was 11000.
  • the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone.
  • the polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated three times in total, and the obtained polymer was analyzed by 19 F-NMR, 1 H-NMR analysis, and IR analysis.
  • Synthesis Example 4 (Synthesis of OH-containing fluorinated allyl ether and vinylidene fluoride copolymer) A 300 ml stainless steel autoclave equipped with a valve, pressure gauge, and thermometer, 34.2 g of AEH1, 200 g of CH 3 CCl 2 F (HCFC-141b), 50 weight of dinormal propyl peroxycarbonate (NPP) A 0.16 g% methanol solution was added, and the inside of the system was sufficiently replaced with nitrogen gas while cooling with a dry ice / methanol solution. Next, 5.8 g of vinylidene fluoride (VdF) was charged from the valve, and the reaction was performed while shaking at 40 ° C. As the reaction progressed, the gauge pressure in the system decreased from 4.4 MPaG before the reaction to 0.98 MPaG after 12 hours.
  • VdF vinylidene fluoride
  • composition ratio of this copolymer was analyzed by 1 H-MNR analysis and 19 F-NMR analysis.
  • the fluorine-containing allyl ether containing VdF / OH group was 55/45 (mol%).
  • number average molecular weight measured by GPC analysis using THF as a solvent was 12000, and the weight average molecular weight was 18000.
  • the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone.
  • the polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated three times in total, and the obtained polymer was analyzed by 19 F-NMR, 1 H-NMR analysis, and IR analysis.
  • MIBK methyl isobutyl ketone
  • the MIBK solution was put in a separating funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water.
  • the organic layer was separated and dried over anhydrous magnesium sulfate.
  • the fluoropolymer (3) was fluid at room temperature and had a number average molecular weight of 5400.
  • the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone.
  • the polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of three times, and the obtained polymer was analyzed by 19 F-NMR, 1 H-NMR analysis, and IR analysis.
  • Example 1 3- (Dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4) in 2.1 g of the polymer obtained in Synthesis Example 2: 0.32 g (theoretical equivalent of hydrosilylation reaction) was added and placed in a constant temperature bath at 40 ° C. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 ⁇ L of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.
  • a platinum-cyclovinylmethylsiloxane complex product number SIP6832.2 manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.
  • Table 1 shows the evaluation results of the viscosity of the liquid composition at 25 ° C. and the appearance of the liquid composition before curing.
  • NF-0100 thinness: 100 ⁇ m
  • NF-0100 thinness 100 ⁇ m
  • NF-0100 thinness 100 ⁇ m
  • a slide glass with a thickness of 1 mm was placed on it, and then at 100 ° C. for 2 hours, followed by 150 ° C. For 1 hour.
  • the release fluororesin film was peeled off to obtain a cured film.
  • the evaluation criteria are as follows. ⁇ : Transparent and uniform. ⁇ : Some cloudiness is observed. X: Opaque and cloudy.
  • the evaluation criteria are as follows. ⁇ : No swelling is visually observed. ⁇ : Swelling is visually observed. X: Dissolve.
  • Example 2 3- (Dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4) in 2.2 g of the polymer obtained in Synthesis Example 3:
  • an insoluble hydrosilylation crosslinking agent (B5) HPL-502 manufactured by Gelest: 0.1g was added and it put into the 50 degreeC thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition.
  • 5 ⁇ L of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.
  • Example 3 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4) in 1.2 g of the polymer obtained in Synthesis Example 4: And 1.2 g of triallyl isocyanurate (TAIC) as a non-silicon-based reactive solvent (D1) were added and placed in a constant temperature bath at 40 ° C. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 ⁇ L of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.
  • TAIC triallyl isocyanurate
  • D1 non-silicon-based reactive solvent
  • Example 4 3- (Dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4) in 2.0 g of the polymer obtained in Synthesis Example 1: 0.16 g and 2.5 g of methyl isobutyl ketone (MIBK) as a non-reactive solvent (D2) were added and placed in a constant temperature bath at 40 ° C. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 ⁇ L of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-type curable composition.
  • MIBK methyl isobutyl ketone
  • D2 non-reactive solvent
  • Example 1 After the solvent was volatilized, it was cured so as to have a thickness of about 100 ⁇ m, then cured in the same manner as in Example 1 except that it was dried at 100 ° C. for 20 minutes, and various physical properties were measured. The results are shown in Table 1.
  • Example 5 3- (Dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4) in 1.0 g of the polymer obtained in Synthesis Example 5: 1.5 g, 1.0 g of triallyl isocyanurate (TAIC) as a non-silicon reactive solvent (D1), and 2.5 g of methyl isobutyl ketone (MIBK) as a non-reactive solvent (D2) It put into the thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 ⁇ L of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-type curable composition.
  • TAIC triallyl isocyanurate
  • MIBK methyl isobutyl ketone
  • Example 6 Tetrakis (dimethylsilyloxy) silane as the soluble hydrosilylation crosslinking agent (B4) used in Example 1: A curable composition was prepared in the same manner as in Example 1 except that was used, and then cured, and various physical properties were measured. The results are shown in Table 1.
  • Example 7 In Example 2, 1,3,5,7-tetramethyl-cyclo-tetrasiloxane as the insoluble hydrosilylation crosslinking agent (B5): A curable composition was prepared in the same manner as in Example 2 except that was used, and then cured, and various physical properties were measured. The results are shown in Table 1.
  • Example 8 A curable composition was prepared in the same manner as in Example 3 except that ethylene glycol diacrylate was used as the non-silicon-based reactive solvent (D1) in Example 3, and then cured, and various physical properties were measured. The results are shown in Table 1.
  • Example 9 A curable composition was prepared in the same manner as in Example 4 except that butyl acetate was used as the non-reactive solvent (D2) in Example 4, and then cured, and various physical properties were measured. The results are shown in Table 1.
  • Example 10 In Example 5, 1.0 g, 1,1,3,3- (dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane was used as the soluble hydrosilylation crosslinking agent (B4). A curable composition was prepared in the same manner as in Example 5 except that 0.2 g of 3-tetramethyldisiloxane was used, and then cured, and various physical properties were measured. The results are shown in Table 1.
  • Comparative Example 1 5 g of the polymer obtained in Synthesis Example 3, 1 g of methyl methacrylate and 4 g of 1H, 1H, 5H-octafluoropentyl acrylate (CH 2 ⁇ CHCOOCH 2 C 4 F 8 H) are dissolved in 1 g of trimethylolpropane triacrylate (TMPA). A uniform composition was obtained. 0.1 g of 2-hydroxy-2-methylpropiophenone was added as a UV initiator to obtain a curable composition.
  • TMPA trimethylolpropane triacrylate
  • NF-0100 thinness: 100 ⁇ m
  • NF-0100 thinness: 100 ⁇ m
  • Comparative Example 2 3- (Dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4) in 2.5 g of the polymer obtained in Comparative Synthesis Example 1: Was added to a constant temperature bath at 40 ° C. Even when taken out after 24 hours, the composition was non-uniform and cloudy. Further, the temperature was raised to 70 ° C., but the non-uniform state did not change.
  • Comparative Example 3 To 2.0 g of the polymer obtained in Comparative Synthesis Example 2, 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a soluble hydrosilylation crosslinking agent (B4): 0.21 g and 2.5 g of methyl isobutyl ketone (MIBK) as a non-reactive solvent (D2) were added and placed in a constant temperature bath at 40 ° C. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 ⁇ L of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-type curable composition.
  • MIBK methyl isobutyl ketone
  • D2 non-reactive solvent
  • Example 1 After the solvent was volatilized, it was cured so as to have a thickness of about 100 ⁇ m, then cured in the same manner as in Example 1 except that it was dried at 100 ° C. for 20 minutes, and various physical properties were measured. The results are shown in Table 1. As is clear from Table 1, the heat resistance was clearly inferior.
  • the curable composition of the present invention gives a transparent cured product having excellent heat resistance. Further, since the refractive index can be controlled by controlling the fluorine content, it can be seen that application to various optical devices is possible.

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Abstract

L'invention porte sur une composition de résine durcissable qui contient : (A) un polymère contenant du fluor qui contient un motif de structure éther d'allyle contenant du fluor (I) ; (B) un agent de réticulation par hydrosilylation ; et (C) un catalyseur d'hydrosilylation. La composition de résine durcissable peut être facilement durcie sans contenir un solvant organique qui ne prend pas part à une réaction d'hydrosilylation.
PCT/JP2010/068331 2009-11-24 2010-10-19 Composition de résine durcissable WO2011065155A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010084150A (ja) * 2002-08-13 2010-04-15 Daikin Ind Ltd 光硬化性含フッ素ポリマーを含む光学材料および光硬化性含フッ素樹脂組成物
WO2012133557A1 (fr) * 2011-03-30 2012-10-04 ダイキン工業株式会社 Composition de résine fluorée pour la soudure d'éléments optiques et produit durci

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059011A1 (fr) * 2000-02-08 2001-08-16 Kaneka Corporation Compositions durcissables
WO2008044765A1 (fr) * 2006-10-12 2008-04-17 Daikin Industries, Ltd. Composition de polymère fluoré durcissable
WO2008153002A1 (fr) * 2007-06-15 2008-12-18 Dow Corning Toray Co., Ltd. Composition polymère durcissable contenant du fluor
JP2009203475A (ja) * 2008-02-28 2009-09-10 Mitsubishi Chemicals Corp 封止樹脂及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059011A1 (fr) * 2000-02-08 2001-08-16 Kaneka Corporation Compositions durcissables
WO2008044765A1 (fr) * 2006-10-12 2008-04-17 Daikin Industries, Ltd. Composition de polymère fluoré durcissable
WO2008153002A1 (fr) * 2007-06-15 2008-12-18 Dow Corning Toray Co., Ltd. Composition polymère durcissable contenant du fluor
JP2009203475A (ja) * 2008-02-28 2009-09-10 Mitsubishi Chemicals Corp 封止樹脂及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010084150A (ja) * 2002-08-13 2010-04-15 Daikin Ind Ltd 光硬化性含フッ素ポリマーを含む光学材料および光硬化性含フッ素樹脂組成物
WO2012133557A1 (fr) * 2011-03-30 2012-10-04 ダイキン工業株式会社 Composition de résine fluorée pour la soudure d'éléments optiques et produit durci
JP2012214754A (ja) * 2011-03-30 2012-11-08 Daikin Industries Ltd 光学素子封止用含フッ素樹脂組成物、及び、硬化物

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