WO2011013720A1 - Oligomère d'uréthane insaturé, composition de résine durcissable, stratifié transparent et son procédé de production - Google Patents

Oligomère d'uréthane insaturé, composition de résine durcissable, stratifié transparent et son procédé de production Download PDF

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WO2011013720A1
WO2011013720A1 PCT/JP2010/062731 JP2010062731W WO2011013720A1 WO 2011013720 A1 WO2011013720 A1 WO 2011013720A1 JP 2010062731 W JP2010062731 W JP 2010062731W WO 2011013720 A1 WO2011013720 A1 WO 2011013720A1
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resin composition
curable resin
polyol
mass
transparent
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PCT/JP2010/062731
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English (en)
Japanese (ja)
Inventor
宜伸 門脇
聡 新山
直子 青木
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旭硝子株式会社
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Priority to JP2011524819A priority Critical patent/JP5737180B2/ja
Priority to CN201080034486.0A priority patent/CN102471449B/zh
Publication of WO2011013720A1 publication Critical patent/WO2011013720A1/fr

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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
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    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
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    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • 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
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    • C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Definitions

  • the present invention relates to a flame retardant unsaturated urethane oligomer suitable for a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates, and a curing containing the unsaturated urethane oligomer.
  • the present invention relates to a curable resin composition, a transparent laminate having a cured resin layer composed of a cured product of the curable resin composition, and a method for producing a transparent laminate using the curable resin composition.
  • a laminated glass in which a pair of glass plates are integrated via an adhesive resin layer is known.
  • the laminated glass is used as a windshield for automobiles because broken glass fragments adhere to the film-like adhesive resin layer and do not scatter.
  • the laminated glass is used as a window glass for buildings (safety glass, crime prevention glass, fire prevention safety glass, etc.) because it is difficult to penetrate and has excellent strength. Therefore, when used as a window glass, the adhesive resin layer may be required to have good flame retardance in addition to excellent transparency.
  • Fireproof safety glass is a glass that functions as a fire door during a fire and functions as a safety glass during normal times.
  • the resin material used for the adhesive resin layer of laminated glass gradually decomposes into low molecular weight substances when the decomposition temperature is reached. If the temperature that decomposes into volatile substances is higher than the ignition temperature of the volatile substances that are generated, it will ignite and ignite. Therefore, the resin material of the adhesive resin layer for fire safety safety glass includes a resin material that suppresses the oxidation reaction of the decomposition product, a resin material that does not volatilize even if the decomposition product is generated, and is crosslinked simultaneously with thermal decomposition. It is necessary to use a resin material that carbonizes by causing a reaction or a cyclization reaction, that is, a resin material having high flame retardancy.
  • the following are proposed as laminated glass using a resin material having high flame retardancy as the resin material of the adhesive resin layer.
  • Fire safety glass using a fluorine-containing copolymer as a resin material for the adhesive resin layer (Patent Document 1).
  • (2) Laminated glass obtained by adding a phosphorus-based flame retardant to the resin material of the adhesive resin layer (Patent Document 2).
  • the flame retardance is improved, but the adhesion between the glass plate and the adhesive resin layer is insufficient. Therefore, a haze value becomes high and it is difficult to use it as a window glass.
  • the laminated glass of (2) since the phosphorus-based flame retardant is not easily mixed with the resin material of the adhesive resin layer, the transparency is impaired or the flame retardancy is not uniform.
  • the amount of phosphorus-based flame retardant added is large, the mechanical properties such as the strength of the adhesive resin layer are impaired, or the added flame retardant migrates inside the adhesive resin layer over time. Problems occur.
  • Patent Document 3 a urethane prepolymer composition using a phosphorus-containing flame retardant polyol as a raw material is disclosed.
  • this urethane prepolymer composition is used for the adhesive resin layer of laminated glass, there is a concern about durability.
  • the following method is known as a manufacturing method of a laminated glass.
  • (I) A method of producing a laminated glass by sandwiching an adhesive resin film between a pair of transparent substrates and thermocompression bonding the laminate.
  • (Ii) A method of manufacturing a laminated glass by injecting a liquid curable resin between a pair of transparent substrates whose periphery is sealed, and then curing the curable resin (Patent Document 4).
  • the method (ii) has a wider variety of curable resins than the method (i), and it is easy to obtain a cured product having various physical properties according to the purpose, and an easily curable resin (especially a photocurable resin). ) Can be used to simplify the manufacturing process.
  • the method (ii) has a drawback that bubbles tend to remain in the resin when the curable resin is injected.
  • a vacuum lamination method As a method for preventing the generation of bubbles, a vacuum lamination method is known.
  • the following method is known as a method for producing laminated glass by the reduced pressure lamination method.
  • a layer of the photocurable resin composition is formed on one transparent substrate, and another transparent substrate is stacked on the layer of the photocurable resin composition under reduced pressure to form a pair of transparent
  • a method for producing a laminated glass, in which a photocurable resin composition is sealed between substrates and then photocured under atmospheric pressure Patent Document 5).
  • a photocurable resin composition containing an unsaturated urethane oligomer As a photocurable resin composition, a photocurable resin composition containing an unsaturated urethane oligomer has been proposed (Patent Document 5). Moreover, the photocurable resin composition containing an unsaturated urethane oligomer is known also as a photocurable resin composition suitable for the method of (iii) (patent document 6). In the photocurable resin composition containing an unsaturated urethane oligomer, the characteristics of the cured product can be adjusted by using an unsaturated urethane oligomer and various monomers in combination. However, the conventional photocurable resin composition cannot obtain a cured product having good flame retardancy.
  • the present invention provides an unsaturated urethane oligomer and a curable resin composition capable of obtaining a cured product having excellent transparency and flame retardancy. Moreover, the curable resin composition used for the method of manufacturing a transparent laminated body is provided. Furthermore, the transparent laminated body which is excellent in transparency and excellent in a flame retardance, and its manufacturing method are provided.
  • the present invention is the following [1] to [15].
  • Polyol component (A1) A polyol component containing the following polyol (a1).
  • Polyol (a1) A polyol having 2 to 3 hydroxyl groups per molecule, a hydroxyl value of 35 to 150 mgKOH / g, and having a phosphorus atom in the molecule.
  • Curable functional group CH 2 ⁇ C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
  • a curable resin composition comprising the unsaturated urethane oligomer (A) of [1] or [2].
  • the curable resin composition according to [3] which is a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates.
  • a transparent laminate having a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates, wherein the cured resin is a curable resin composition of [4] to [8] A transparent laminate that is a cured product of the above. [10] The transparent laminate according to [9], wherein at least one of the pair of transparent substrates is a glass plate.
  • a pair of transparent substrates and the pair of transparent substrates are formed between the pair of transparent substrates in a reduced-pressure atmosphere by forming a sealed space in which the curable resin composition of [4] to [8] is accommodated.
  • a first step of producing a laminated precursor having the curable resin composition sealed in between, and the laminated precursor is placed in an atmosphere having a pressure higher than the reduced-pressure atmosphere, and the curing is performed in the atmosphere.
  • the manufacturing method of a transparent laminated body which has a 2nd process of hardening an adhesive resin composition.
  • the method according to [11] wherein the reduced-pressure atmosphere is a pressure atmosphere of 100 Pa or less, and the atmosphere having a higher pressure than the reduced-pressure atmosphere is an atmospheric pressure atmosphere.
  • the curable resin composition is a photocurable resin composition, and in the second step, the laminated precursor is irradiated with light to cure the curable resin composition.
  • Manufacturing method is a photocurable resin composition, and in the second step, the laminated precursor is irradi
  • a curable resin composition comprising the unsaturated urethane oligomer (A) of [14].
  • a cured product having excellent transparency and flame retardancy can be obtained.
  • a curable resin composition of the present invention a cured product having excellent transparency and flame retardancy can be obtained.
  • the transparent laminate of the present invention is excellent in transparency and flame retardancy. According to the method for producing a transparent laminate of the present invention, a transparent laminate having excellent transparency and excellent flame retardancy can be produced.
  • the curable functional group represented by CH 2 ⁇ C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group) is an acryloyloxy group (where R is a hydrogen atom). Or a methacryloyloxy group (when R is a methyl group), and the group represented by the formula is also referred to as a (meth) acryloyloxy group.
  • (meth) acrylate is used as a general term for “acrylate” and “methacrylate”.
  • the unsaturated urethane oligomer (A) of the present invention is a urethane (meth) acrylate oligomer having an average of 2 to 4 curable functional groups described below per molecule and a phosphorus content of 1 to 6% by mass.
  • Curable functional group CH 2 ⁇ C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
  • the unsaturated urethane oligomer (A) is suitable as one component of a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates. It is. Since the unsaturated urethane oligomer (A) has a phosphorus atom in the molecule, the cured product has flame retardancy.
  • the average number of curable functional groups per molecule of the unsaturated urethane oligomer (A) is 2 to 4, and preferably 2 to 3. If the average number of curable functional groups is 2 or more, a crosslinked structure can be introduced into a part of the cured resin layer, heat resistance is increased, and the cured resin layer is less likely to flow and deform when exposed to high temperatures. If the average number of curable functional groups is 4 or less, the crosslink density will not be too high, the flexibility of the cured resin layer will be good, and the impact resistance will be good.
  • the average number of curable functional groups per molecule of the unsaturated urethane oligomer (A) is the number of hydroxyl groups of the polyol component (A1), the number of isocyanate groups of the polyisocyanate compound (A2), and the curability of the unsaturated hydroxy compound (A3). It is adjusted by the number of functional groups and the number of hydroxyl groups. Diisocyanate having 2 isocyanate groups is preferable as the polyisocyanate compound (A2), and unsaturated monool having 1 curable functional group is preferable as the unsaturated hydroxy compound (A3).
  • the average number of curable functional groups per molecule of the obtained unsaturated urethane oligomer (A) is usually substantially the same as the average number of hydroxyl groups per molecule of the polyol component (A1).
  • an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 can be obtained.
  • diol and triol as the polyol component (A1), an unsaturated urethane oligomer (A) having an average curable functional group number between 2 and 3 is obtained, and only triol is obtained as the polyol component (A1).
  • an unsaturated urethane oligomer (A) having an average number of curable functional groups of 3 is obtained.
  • a plurality of curable functional groups present in one molecule may be the same or different. However, usually, when having a plurality of curable functional groups in one molecule, it is preferable that they have the same curable functional group.
  • the curable functional group in the unsaturated urethane oligomer (A) is preferably an acryloyloxy group.
  • the curable functional group in the unsaturated urethane oligomer (A) tends to be less reactive as the unsaturated urethane oligomer (A) has a higher molecular weight, and when used in combination with a relatively low molecular weight compound, both cure.
  • the curable functional group in the unsaturated urethane oligomer (A) is high. Therefore, the curable functional group in the unsaturated urethane oligomer (A) is preferably an acryloyloxy group having a higher reactivity than the methacryloyloxy group.
  • the phosphorus content in the unsaturated urethane oligomer (A) (100% by mass) is 1 to 7% by mass, preferably 1 to 4% by mass.
  • the phosphorus content is 1% by mass or more, a sufficient flame retardant effect can be obtained.
  • the phosphorus content is 7% by mass or less, there is no generation of heterogeneous oligomers due to high molecular weight (gelation) of oligomers or lowering of compatibility during the production of unsaturated urethane oligomer (A), and curing. Since the cured
  • the unsaturated urethane oligomer (A) is a reaction product of the polyol component (A1), the polyisocyanate compound (A2), and the unsaturated hydroxy compound (A3).
  • Examples of a method for obtaining the reaction product include the following: Examples thereof include the methods (1) to (3). (1) A method in which a polyol component (A1), a polyisocyanate compound (A2), and an unsaturated hydroxy compound (A3) are simultaneously reacted. (2) After reacting the polyisocyanate compound (A2) and the unsaturated hydroxy compound (A3) in a stoichiometrically excessive condition with an isocyanate group, the resulting reaction product is further reacted with a polyol component (A1). How to make.
  • the method (1) is easy, variations in the molecular weight and viscosity of the unsaturated urethane oligomer (A) are easily observed, which is not industrially preferable.
  • the method (2) when the number of hydroxyl groups in the polyol component (A1) is 3 or more, an ultrahigh molecular weight product (gel component) is hardly generated.
  • the method (3) is industrially preferable because a qualitative unsaturated urethane oligomer (A) can be obtained constantly.
  • Examples of the method (3) include a method having the following step (3-1) and step (3-2).
  • (3-1) If necessary, the polyol component (A1) and the polyisocyanate compound (A2) are reacted in the presence of a stoichiometric excess of isocyanate groups in the presence of a urethanization catalyst to obtain an isocyanate group-terminated urethane prepolymer. Obtaining.
  • (3-2) A step of reacting the unsaturated hydroxy compound (A3) with an isocyanate group at the terminal of the urethane prepolymer in the presence of a polymerization inhibitor as necessary.
  • Step (3-1) Examples of urethanization catalysts include cobalt naphthenate, zinc naphthenate, zinc 2-ethylhexanoate, dibutyltin dilaurate, tin 2-ethylhexanoate, triethylamine, 1,4-diabicyclo [2.2.2] octane, and the like. It is done.
  • the ratio of the polyol component (A1) and the polyisocyanate compound (A2) is preferably such that the molar ratio of isocyanate group: hydroxyl group is 1.2: 1 to 3: 1, and is 1.2: 1 to 2: 1. Is more preferred.
  • the reaction temperature is preferably a temperature in a normal urethanization reaction, that is, 30 to 90 ° C.
  • the polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-hydroquinone, o-nitrotoluene and the like.
  • the amount of the polymerization inhibitor is preferably 50 to 5,000 ppm based on the unsaturated hydroxy compound (A3).
  • the ratio of the urethane prepolymer and the unsaturated hydroxy compound (A3) is preferably such that the molar ratio of isocyanate group: hydroxyl group is 1: 1 to 1: 1.5.
  • the reaction temperature is preferably 30 to 90 ° C.
  • the polyol component (A1) is a polyol component containing a polyol (a1) having a phosphorus atom in the molecule as an essential component, preferably further containing a polyol (a2), and if necessary, another polyol (a3). May be included.
  • the phosphorus content in the polyol component (A1) (100% by mass) is more than 1% by mass, preferably 10% by mass or less, and more preferably 1.1 to 8.5% by mass.
  • the polyol component (A1) having a phosphorus content exceeding 1% by mass the phosphorus content in the unsaturated urethane oligomer (A) can be made 1% by mass or more.
  • the polyol component (A1) having a phosphorus content exceeding 10% by mass can be used, the compatibility with other components may be lowered, and the compatibility can be reduced by setting the phosphorus content to 10% by mass or less. It can be set as a favorable polyol component (A1).
  • the polyol (a1) is a polyol having 2 to 3 hydroxyl groups per molecule and a hydroxyl value of 35 to 150 mgKOH / g and having a phosphorus atom in the molecule.
  • a polyol (a1) may be used individually by 1 type, and may use 2 or more types together.
  • the polyol (a1) can be obtained as a commercial product.
  • “FC450” (number of hydroxyl groups: 2, hydroxyl value: 450 mgKOH / g, phosphorus content: 7.2 mass%) manufactured by Adeka Corporation, “Weston 430” manufactured by Weston Chemical Co., Ltd. (number of hydroxyl groups: 3, hydroxyl value: 395 mg KOH / g, phosphorus content: 12.0 mass%)
  • “Nonen R0412-15” manufactured by Maruhishi Oil Chemical Co., Ltd.
  • the number of hydroxyl groups per molecule of the polyol (a1) is 2 to 3, and 2 is preferable. If the number of hydroxyl groups per molecule of the polyol (a1) is 2 to 3, an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 to 4 can be easily obtained.
  • the hydroxyl value of the polyol (a1) is 35 to 150 mgKOH / g, preferably 40 to 145 mgKOH / g. If the hydroxyl value of the polyol (a1) is 35 mgKOH / g or more, the molecular weight of the polyol (a1) does not become too large, so that the viscosity of the polyol (a1) does not become too large, and there is no problem in workability. When the hydroxyl value of the polyol (a1) is 145 mgKOH / g or less, the compatibility with the monomer (B) is improved and the transparency of the cured product is improved. The hydroxyl value of the polyol (a1) is measured according to JIS K1557-1 (2007 edition). The same applies to the hydroxyl value of other polyols.
  • the polyol (a2) is a polyoxyalkylene polyol having 2 hydroxyl groups per molecule and a hydroxyl value of 20 to 120 mgKOH / g and having no phosphorus atom in the molecule.
  • the polyol (a2) is a polyol having a polyoxyalkylene chain comprising an oxyalkylene group, and is preferably a polyoxyalkylene polyol obtained by ring-opening addition polymerization of a monoepoxide as an initiator in the presence of a catalyst.
  • a polyol (a2) may be used individually by 1 type, and may use 2 or more types together.
  • the catalyst examples include diethyl zinc, iron chloride, metal porphyrin, double metal cyanide complex, cesium compound, alkali (earth) metal compound and the like, and double metal cyanide complex is preferable.
  • a polyoxyalkylene polyol having a low hydroxyl value is obtained by reacting propylene oxide with a general-purpose alkali metal compound catalyst (potassium hydroxide, etc.)
  • the isomerization reaction of propylene oxide easily occurs and the degree of unsaturation increases.
  • a cured product containing an unsaturated urethane oligomer (A) obtained using a polyoxyalkylene polyol having a high degree of unsaturation may have insufficient mechanical properties.
  • the unsaturation degree of the polyol (a2) is preferably 0.05 meq / g or less.
  • the double metal cyanide complex a complex mainly composed of zinc hexacyanocobaltate is preferable, and an ether and / or alcohol complex of zinc hexacyanocobaltate is particularly preferable.
  • the ether and / or alcohol complex of zinc hexacyanocobaltate include those described in JP-B-46-27250.
  • the ether ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether and the like are preferable, and glyme is particularly preferable from the viewpoint of easy handling at the time of producing the complex.
  • the alcohol tert-butanol, tert-butyl cellosolve and the like are preferable.
  • the number of active hydrogens in the initiator is 2.
  • the active hydrogen means an active hydrogen atom that can react with a monoepoxide, such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group.
  • a monoepoxide such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group.
  • a hydrogen atom of a hydroxyl group is preferable. Therefore, a polyhydroxy compound having 2 hydroxyl groups is preferable as the initiator.
  • the initiator examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and a polyol (a2) obtained by reacting these with alkylene oxide And lower molecular weight polyoxyalkylene polyols.
  • the molecular weight of the initiator is preferably 500 to 1,500.
  • An initiator may be used individually by 1 type and may use 2 or more types together.
  • Monoepoxide is a compound having one epoxy ring.
  • the monoepoxide include alkylene oxide, glycidyl ether, glycidyl ester and the like, and alkylene oxide is preferable.
  • the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and the like, and ethylene oxide and propylene oxide are preferable.
  • a monoepoxide may be used individually by 1 type and may use 2 or more types together. When two or more kinds of monoepoxides are used in combination, any polymerization method of block polymerization and random polymerization may be used, and both block polymerization and random polymerization may be combined.
  • the polyol (a2) is preferably a polyoxypropylene polyol obtained using only propylene oxide as a monoepoxide, or a poly (oxypropylene / oxyethylene) polyol obtained using propylene oxide and a small amount of ethylene oxide as a monoepoxide.
  • Examples of the polyoxyalkylene polyol other than the polyoxyalkylene polyol obtained by reacting a monoepoxide with an initiator include polyoxytetramethylene polyol.
  • the number of hydroxyl groups per molecule of polyol (a2) is 2. If the number of hydroxyl groups per molecule of the polyol (a2) is 2, an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 to 4 can be easily obtained.
  • the hydroxyl value of the polyol (a2) is 20 to 120 mgKOH / g. If the hydroxyl value is within this range, the molecular weight of the polyol (a2) is not too large and the viscosity can be suppressed, which is industrially useful.
  • the hydroxyl value of the polyol (a2) is 20 mgKOH / g or more, the compatibility with the polyol (a1) is good, and the cured product obtained by curing the curable composition has sufficient transparency.
  • the hydroxyl value of the polyol (a2) is 120 mgKOH / g or less, the compatibility with the monomer (B) and the like is good, and the cured product has sufficient transparency.
  • the proportion of the polyol (a2) is adjusted so that the phosphorus content in the polyol component (A1) (100% by mass) is 1 to 7% by mass.
  • the proportion of the polyol (a2) is preferably 0.2 to 4 mol, more preferably 0.4 to 2.5 mol, relative to 1 mol of the polyol (a1). If the ratio of a polyol (a2) is this range, it can be compatible with transparency and flame retardance of the hardened
  • the polyol (a3) is a polyol that is neither the polyol (a1) nor the polyol (a2).
  • Examples of the polyol (a3) include polyoxyalkylene polyols having 3 or more hydroxyl groups.
  • polyols such as a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, are mentioned.
  • the polyol (a3) is not an essential component, and the proportion of the polyol (a3) is adjusted so that the phosphorus content in the polyol component (A1) (100% by mass) is 1 to 7% by mass.
  • the mass ratio in a polyol component (A1) shall be a small quantity.
  • the proportion of the polyol (a3) is preferably 25% by mass or less, more preferably 10% by mass or less, out of 100% by mass of the polyol component (A1).
  • the polyisocyanate compound (A2) is obtained by modifying alicyclic polyisocyanates, aliphatic polyisocyanates, aromatic ring-containing aliphatic polyisocyanates having an average number of isocyanate groups of 2 or more per molecule, and aromatic ring-containing aliphatic polyisocyanates. Examples thereof include modified polyisocyanates.
  • An aromatic polyisocyanate having an isocyanate group bonded to an aromatic ring is preferably not used because it has a high possibility of causing yellowing of a cured product.
  • the average number of isocyanate groups per molecule of the polyisocyanate compound (A2) is preferably 2 to 4, and 2 is particularly preferable. That is, as the polyisocyanate compound (A2), diisocyanate is preferable.
  • a polyisocyanate compound (A2) may be used individually by 1 type, and may use 2 or more types together.
  • polyisocyanate compound (A2) examples include diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, a prepolymer modified product, a nurate modified product, a urea modified product, and a carbodiimide modified product of the diisocyanate. And isophorone diisocyanate and hexamethylene diisocyanate are particularly preferable.
  • the unsaturated hydroxy compound (A3) is a compound having a curable functional group and a hydroxyl group, and two or more curable functional groups may be present in one molecule, and two or more hydroxyl groups are present in one molecule. It may be.
  • a compound having one curable functional group and one hydroxyl group per molecule is preferred.
  • the unsaturated hydroxy compound (A3) is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 1 to 10 carbon atoms, more preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 1 to 5 carbon atoms.
  • the curable functional group is preferably an acryloyloxy group. Therefore, the unsaturated hydroxy compound (A3) is more preferably a hydroxyalkyl acrylate having a hydroxyalkyl having 1 to 5 carbon atoms.
  • the unsaturated hydroxy compound (A3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, and the like.
  • 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred, Hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferred.
  • An unsaturated hydroxy compound (A3) may be used individually by 1 type, and may use 2 or more types together.
  • the curable resin composition of the present invention is a composition containing an unsaturated urethane oligomer (A).
  • the curable resin composition sandwiched between a pair of transparent substrates, which will be described later, is cured to form a transparent laminate. It is suitable as a curable resin composition used in the production method.
  • the curable resin composition containing the unsaturated urethane oligomer (A) can be used for adhesives, coating agents, and other applications.
  • Various additives can be added to the curable resin composition depending on the application. It is usually essential to add a curing agent for curing the curable resin composition, and a radical generator or a photopolymerization initiator is preferable as the curing agent.
  • a curable resin composition containing a curing agent that generates radicals by heat is a thermosetting type
  • a curable resin composition containing a photopolymerization initiator is a photocurable type.
  • the curable resin composition containing the unsaturated urethane oligomer (A) monomers such as a monomer (B) and other monomers (F) described later are blended for adjusting the physical properties of the cured product. It is preferable.
  • a monomer a compound having 1 to 6 curable functional groups is preferable, and a compound having 1 to 2 curable functional groups is more preferable. From the viewpoint of obtaining a hard cured product, a compound having 3 to 6 curable functional groups is preferred.
  • a low viscosity compound is preferable as a monomer from the point which improves the applicability
  • Various additives that do not participate in the reaction may be added to the curable resin composition.
  • this additive the below-mentioned additive (G) etc. are mentioned, for example.
  • the curable resin composition is applied using a solvent, and then the curable resin composition is cured by removing the solvent.
  • no solvent is used.
  • the curable resin composition used in the method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates according to the present invention comprises an unsaturated urethane oligomer (A) as an essential component. It is preferable that the monomer (B), the monomer (C), the photopolymerization initiator (D), and / or other unsaturated oligomers (E) are further contained, and if necessary, other monomers
  • the body (F), additive (G), etc. may further be included.
  • the unsaturated urethane oligomer (A) is preferably added so that the phosphorus content in the curable resin composition (100% by mass) is 0.1 to 5% by mass, and 0.1 to 3% by mass. It is more preferable to add so that it becomes. If phosphorus content is 0.1 mass% or more, the hardened
  • the unsaturated urethane oligomer (A) is preferably 10 to 100 parts by mass, more preferably 40 to 60 parts by mass, out of a total of 100 parts by mass of the components (A) to (C), (E) and (F). If unsaturated urethane oligomer (A) is 10 mass parts or more, the flame retardance of hardened
  • the monomer (C) When the monomer (C) is included, 3 to 50 parts by mass is preferable, and 5 to 25 parts by mass is preferable among 100 parts by mass in total of the components (A) to (C), (E) and (F). More preferred. If the ratio of a monomer (C) is 3 mass parts or more, the softness
  • oligomer (E) When other oligomer (E) is included, 3 to 55 parts by mass is preferable, and 30 to 50 parts by mass is preferable among 100 parts by mass of the total of components (A) to (C), (E) and (F). More preferred. When the ratio of the other oligomer (E) is 3 parts by mass or more, the flexibility of the cured product is improved and the viscosity of the curable resin composition can be lowered, which is industrially useful. When other monomer (F) is included, 50 parts by mass or less is preferable and 100 parts by mass or less is preferable among the total 100 parts by mass of components (A) to (C), (E) and (F). More preferred. When the additive (G) is included, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less with respect to 100 parts by mass in total of the components (A) to (C), (E) and (F). .
  • the monomer (B) is a compound represented by CH 2 ⁇ C (R) C (O) O—R 2 (where R is a hydrogen atom or a methyl group, and R 2 has 1 to 2 hydroxyl groups) And a hydroxyalkyl group having 3 to 4 carbon atoms.
  • the monomer (B) is effective as a component that increases the hydrophilicity of the cured product of the curable resin composition and improves the affinity between the cured product and the surface of the transparent substrate (glass plate). By using (B), the adhesion between the cured product and the transparent substrate is improved.
  • the monomer (B) is a (meth) acrylate having a hydroxyalkyl group or a dihydroxyalkyl group, and is preferably a methacrylate in order to proceed the reaction with the unsaturated urethane oligomer (A) uniformly. That is, even if the curable functional group of the unsaturated urethane oligomer (A) is an acryloyloxy group, the reactivity is low, and if the curable functional group of the monomer (B) is an acryloyloxy group, both curable functional groups There is a possibility that a difference in reactivity between groups becomes large and uniform curing cannot be obtained.
  • a monomer (B) may be used individually by 1 type, and may use 2 or more types together.
  • the number of hydroxyl groups of the monomer (B) is 2 or less, the cured product is hardly brittle. Accordingly, the number of hydroxyl groups in R 2 is 1 to 2, and more preferably 1.
  • the number of carbon atoms in R 2 of the monomer (B) is 3-4.
  • R 2 has 3 or more carbon atoms, the compatibility with the unsaturated urethane oligomer (A) having a long chain structure is good, and a cured product obtained by curing the curable composition has sufficient transparency.
  • the carbon number of R 2 is 4 or less, the hydroxyl group density becomes high and sufficient adhesion can be obtained.
  • Examples of the monomer (B) include 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and the like, and 2-hydroxybutyl methacrylate is preferable.
  • the monomer (C) is a compound represented by CH 2 ⁇ C (R) C (O) O—R 3 (wherein R is a hydrogen atom or a methyl group, and R 3 has 8 to 22 carbon atoms) It is an alkyl group of
  • the monomer (C) is preferably methacrylate, but the monomer (C) has a higher molecular weight than the monomer (B), so it may be An acrylate may also be used.
  • a monomer (C) may be used individually by 1 type, and may use 2 or more types together.
  • the curable resin composition contains the monomer (C)
  • the elastic modulus of the cured product is lowered, and the tear resistance is easily improved.
  • carbon number of an alkyl group is 8 or more, there is little volatility and the glass transition temperature of hardened
  • the carbon number of the alkyl group is 22 or less, the alcohol component of the raw material can be easily obtained via a natural product and is more industrial.
  • Examples of the monomer (C) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate and the like, and n-dodecyl methacrylate and n-octadecyl methacrylate are particularly preferable.
  • Photopolymerization initiator (D) When the curable resin composition of this invention contains a photoinitiator (D), it becomes a photocurable resin composition.
  • the photopolymerization initiator (D) those which are excited by irradiation with visible light or ultraviolet light (wavelength 300 to 400 nm) and are activated to accelerate the curing reaction are preferable.
  • photopolymerization initiator (D) examples include benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, acetophenone, 3-methylacetophenone, benzoyl, benzoin isobutyl ether, benzoin Isopropyl ether, benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like, such as 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2- Hydro Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan
  • An acyl phosphine oxide-based photopolymerization initiator such as bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide is particularly preferable from the viewpoint of curing the conductive resin composition.
  • a photoinitiator (D) may be used individually by 1 type, and may use 2 or more types together.
  • the curable resin composition of the present invention may contain a small amount of an unsaturated oligomer (E) other than the unsaturated urethane oligomer (A) for the purpose of adjusting the viscosity of the composition and the physical properties of the cured product.
  • unsaturated oligomers (E) include urethane (meth) acrylate oligomers obtained using polyols that do not contain phosphorus atoms, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, and the like. Can be mentioned.
  • the curable resin composition of the present invention is a monomer (F) ((meth) acrylate other than the monomer (B) and the monomer (C) for the purpose of adjusting the physical properties of the resulting cured product. Etc.) may be included in a small amount.
  • the other monomer (F) include poly (meth) acrylate of polyhydric alcohol.
  • the curable resin composition contains a low boiling point compound.
  • the method of injecting and curing a liquid curable resin composition between a pair of transparent substrates sealed at the periphery even when injecting with a reduced pressure between the transparent substrates, it is exposed to a reduced pressure at the time of injection. Since the surface area of the curable resin composition is narrow and the degree of vacuum need not be so high, volatilization is a problem even if the curable resin composition contains a compound having a relatively low boiling point. There are few.
  • the curable resin composition is exposed to reduced pressure in a state where the curable resin composition spreads over almost the entire surface excluding the peripheral portion of the transparent substrate.
  • the disappearance due to volatilization is severe, and the composition of the curable resin composition may change greatly.
  • the monomer (B) is a hydroxyalkyl (meth) acrylate and has a sufficiently high boiling point. Further, the monomer (C) has a higher boiling point than the alkyl group having a large number of carbon atoms, even if it is an alkyl (meth) acrylate. Alkyl (meth) acrylates having a low carbon number of the alkyl group often have a low boiling point, and the curable resin composition containing such a low boiling point alkyl (meth) acrylate as another monomer (F) is: It cannot be used as a curable resin composition for producing a transparent laminate by a reduced pressure lamination method.
  • the curable resin composition that can be used in the reduced pressure lamination method preferably does not contain a monomer having a normal pressure boiling point of 150 ° C. or lower, preferably 200 ° C. or lower.
  • additive (G) examples include ultraviolet absorbers (benzotriazoles, hydroxyphenyltriazines, etc.), light stabilizers (hindered amines, etc.), pigments, dyes, metal oxide fine particles, fillers, and the like.
  • the viscosity of the curable resin composition used in the method for producing a transparent laminate likewise the viscosity of the present invention curable resin composition which can be used in other applications, the viscosity V 40 at 40 ° C. It is preferably 50 Pa ⁇ s or less.
  • the viscosity V 25 at 25 ° C. is preferably 0.05 Pa ⁇ s or more.
  • the viscosity is measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U).
  • V 40 When the viscosity V 40 is 50 Pa ⁇ s or less, the fluidity is good, and when used in the reduced pressure laminating method described later, bubbles that do not easily disappear in the curable resin composition are hardly generated.
  • the curable resin composition is used for an application in which a solvent can be used, the solvent is added to increase fluidity to perform application, etc., and then the curable resin composition obtained by removing the solvent is cured. Can be made.
  • V 25 of the curable resin composition is 0.05 Pa ⁇ s or more, the physical properties of the cured product are improved.
  • the specific unsaturated urethane oligomer (A) obtained by using the specific polyol component (A1) described above Therefore, when the composition is cured, a cured product having excellent transparency and flame retardancy is obtained.
  • the curable resin composition of the present invention is preferably used as a curable resin composition for producing a transparent laminate described later.
  • the present invention is not limited to this application, and can be used for other applications as a curable resin, particularly as a photocurable resin.
  • An example of such a laminate is a solar cell module.
  • at least one substrate is transparent so that light necessary for curing the photocurable resin composition can be incident thereon.
  • thermosetting resin composition can be used for thermosetting, but even if the opaque substrate is opaque to visible light, for example against ultraviolet rays necessary for photocuring. If it is transparent, a photocurable resin composition can be used even if both surfaces are opaque substrates.
  • a transparent substrate with low light transmittance a glass substrate on which a thin film solar cell is formed is used, and a layer made of a cured product of the curable resin composition of the present invention is formed between the glass substrate and a solar cell module.
  • a layer made of a cured product of the curable resin composition of the present invention is formed between the glass substrate and a solar cell module.
  • cured material of the curable resin composition of this invention a flame retardance performance can be provided to a solar cell module, and safety
  • a power generation layer made of thin film silicon can be provided on both glass substrates, or a thin film silicon substrate and a glass substrate on which a compound semiconductor thin film is formed can be combined and laminated.
  • both substrates such as a glass substrate may be transparent.
  • a plurality of solar cell substrates made of single crystal silicon or microcrystalline silicon are arranged between a pair of glass substrates, and the solar cell substrate is interposed between the glass substrates by a cured product of the curable resin composition of the present invention. It can also be enclosed.
  • One side of the glass substrate may be a waterproof resin sheet.
  • Such a solar cell module has flame retardancy, and safety is improved when it is installed in a building.
  • even if a part of the solar cell substrate to be encapsulated is defective and excessive current flows to generate heat, it is encapsulated by using the cured product of the curable resin composition of the present invention as the encapsulating resin. Since the resin has flame retardancy, safety can be improved.
  • the transparent laminate of the present invention has a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates.
  • this transparent laminated body and this transparent substrate mean that it is transparent with respect to visible light.
  • the transparent substrate examples include a glass plate or a resin plate. If a glass plate is used, a laminated glass is obtained. If a polycarbonate plate is used as the resin plate, a lightweight transparent panel having high impact resistance can be obtained. Further, a glass plate and a resin plate may be used in combination.
  • the size of the transparent substrate is not particularly limited, but can be widely used as a transparent member to be installed in an opening for a building or a vehicle if it is a transparent substrate having at least one side of 300 mm or more, more preferably 600 mm or more. . In normal applications, a size of 4 m 2 or less is appropriate.
  • the layer of the cured resin contained in the transparent laminate is a layer made of a cured product of the curable resin composition of the present invention.
  • the thickness of the cured resin layer is preferably 0.2 to 4.0 mm. When the thickness of the cured resin layer is 0.2 mm or more, the mechanical strength of the transparent laminate is good. When the thickness of the cured resin layer is 4.0 mm or less, the transparent laminate is excellent in transparency and can be used as a window glass.
  • the cured resin layer sandwiched between the transparent substrates is made of a cured product of the curable resin composition of the present invention, and thus has excellent transparency and flame retardancy. Excellent in properties.
  • the transparent laminate of the present invention can be produced by a known production method (for example, a method of sandwiching a curable resin composition between a pair of transparent substrates and curing the curable resin composition). It is preferable to manufacture by a reduced pressure lamination method using a curable resin composition.
  • the decompression lamination method itself is described in International Publication No. 2008/081838 and International Publication No. 2009/016943.
  • the feature of the reduced pressure lamination method is that a curable resin composition layer is formed on one transparent substrate, and another transparent substrate is stacked on the curable resin composition layer in a reduced pressure atmosphere.
  • the curable resin composition is hermetically sealed between the transparent substrates and then placed in a pressure atmosphere (usually an atmospheric pressure atmosphere) higher than the reduced-pressure atmosphere to cure the curable resin composition.
  • a pressure atmosphere usually an atmospheric pressure atmosphere
  • 1st process The said hardening which formed the sealed space which accommodated the curable resin composition inside between a pair of transparent substrates in a pressure-reduced atmosphere, and was sealed between a pair of transparent substrates and this pair of transparent substrates.
  • 2nd process The process of putting the said lamination
  • the reduced pressure atmosphere in the first step is preferably a pressure atmosphere of 1 kPa or less, and more preferably a pressure atmosphere of 100 Pa or less. Further, if the pressure in the reduced-pressure atmosphere is too low, the curable resin composition such as a monomer may be volatilized. Therefore, the reduced-pressure atmosphere is preferably a pressure atmosphere of 1 Pa or more, and more preferably a pressure atmosphere of 10 Pa or more.
  • the atmosphere having a higher pressure than the reduced-pressure atmosphere in the second step is preferably a pressure atmosphere of 50 kPa or more, and more preferably a pressure atmosphere of 100 kPa or more.
  • the pressure atmosphere in the second step is usually an atmospheric pressure atmosphere.
  • the production method will be described by taking as an example the case where the atmosphere having a higher pressure than the reduced pressure atmosphere is an atmospheric pressure atmosphere.
  • the bubbles are likely to disappear before the curable resin composition is cured, and a cured resin layer having no bubbles is easily obtained.
  • the laminated precursor formed in the first step is placed under atmospheric pressure, pressure is also applied to the curable resin composition in the sealed space due to the pressure from the transparent substrate under atmospheric pressure.
  • the inside of the bubbles in the curable resin composition is at the reduced-pressure atmospheric pressure in the first step, the volume of the bubbles is reduced by the pressure applied to the curable resin composition in the second step. When this gas dissolves in the curable resin composition, the bubbles disappear.
  • the lamination precursor In order to eliminate bubbles, it is preferable to hold the lamination precursor under atmospheric pressure for a while before the curable resin composition is cured.
  • the holding time is preferably 5 minutes or more, but the holding time may be shorter when there are no bubbles or when the bubbles are very small and quickly disappear.
  • the reduced pressure atmosphere is required at the stage of forming the sealed space, and is not required at the stage before that.
  • a sealing material having a predetermined thickness is provided around the periphery of one surface of one transparent substrate, and the curable resin composition is supplied to the surface of the transparent substrate in a region surrounded by the sealing material to be curable.
  • these steps can be performed in an atmospheric pressure atmosphere.
  • the sealed space is preferably formed as follows.
  • the transparent substrate having the layer of the curable resin composition obtained as described above and the other transparent substrate are put in a reduced pressure chamber and set in a predetermined arrangement. That is, a transparent substrate having a layer of a curable resin composition was placed on a horizontal surface plate with the layer of the curable resin composition facing up, and the other transparent substrate was attached to the tip of a cylinder that could be moved up and down. It attaches to the lower surface of a horizontal surface plate, and both transparent substrates are located in parallel, without making the layer of curable resin composition contact the other transparent substrate. Thereafter, the decompression chamber is closed and evacuated, and the inside of the decompression chamber is set to a predetermined decompressed atmosphere.
  • the cylinder After the inside of the decompression chamber becomes a predetermined decompression atmosphere, the cylinder is operated and both transparent substrates are overlapped via the layer of the curable resin composition, and the curable resin is placed in the space surrounded by the both transparent substrates and the sealing material. The composition is sealed to form a laminated precursor. After forming the lamination precursor, the inside of the reduced pressure chamber is returned to the atmospheric pressure atmosphere, and the lamination precursor is taken out from the reduced pressure chamber.
  • the adhesion strength between the transparent substrates and the sealing material may be such that no gas enters from the interface between the transparent substrate and the sealing material when the laminated precursor is placed under atmospheric pressure.
  • a layer of a pressure sensitive adhesive can be provided on the surface of the sealing material to adhere the transparent substrate and the sealing material.
  • a curable adhesive is provided at the interface between the transparent substrate and the sealing material, or the sealing material is formed of a curable resin to form a laminated precursor, and then taken out from the vacuum chamber or from the vacuum chamber. Thereafter, the adhesive strength between the transparent substrate and the sealing material can be increased by curing the curable adhesive or the curable resin.
  • the second step is a step of placing the lamination precursor under atmospheric pressure and curing the curable resin composition.
  • the curable resin composition is a thermosetting curable resin, it is thermoset. More preferably, a photocurable resin composition is used as the curable resin composition and photocured. Photocuring can be performed by irradiating light from a light source such as an ultraviolet lamp through a transparent substrate. The light irradiation is preferably performed for 3 to 30 minutes. As described above, it is preferable to harden the curable resin composition after holding the laminated precursor for a while under atmospheric pressure. By curing the curable resin composition, the curable resin composition becomes a cured resin, and the transparent laminate as described above is obtained.
  • Examples 1 to 12 are examples, and examples 13 to 16 are comparative examples.
  • the phosphorus content in each sample was measured by atomic absorption spectrometry using an inductively coupled plasma emission spectrophotometer (Seiko Instruments, SPS3100).
  • the transmittance was measured as an evaluation of the transparency of the portion where the cured resin layer of the transparent laminate was present.
  • the transmittance was measured according to ASTM D1003 using Hazeguard II (manufactured by Toyo Seiki Seisakusho).
  • the transmittance of the transparent laminate is preferably 90% or more from the viewpoint of clear visibility when used as a laminated glass, for example.
  • the temperature chamber was heated so that the temperature profile was almost the same as the temperature profile defined by the Cabinet Order of Article 109-2 of the Building Standards Act, Article 2, Item 9 of the Building Standards Act.
  • the case where no flame was generated from the non-heated surface was evaluated as “pass”; the case where the flame was generated from the non-heated surface was determined as “fail”.
  • Polyol (c-4) “Nonen R0811-9” manufactured by Maruhishi Oil Chemical Co., Ltd. (number of hydroxyl groups: 2, hydroxyl value: 142 mgKOH / g, phosphorus content: 12.0% by mass).
  • Polyol (a2) Polyol (d-1): Zinc hexacyanocobaltate-glyme complex was used as a catalyst, propylene oxide was reacted with an initiator to deactivate the catalyst, and then potassium hydroxide was used as a catalyst to react with ethylene oxide. The catalyst was deactivated and purified to obtain a polyoxyalkylene polyol (hydroxyl number: 2, hydroxyl value: 28 mgKOH / g, oxyethylene group ratio: 24% by mass).
  • Polyol (d-2) Polyoxyalkylene polyol (hydroxyl number: 2, hydroxyl value: 112 mgKOH / g) was obtained by reacting propylene oxide with an initiator using potassium hydroxide as a catalyst and purifying.
  • Polyol component (A1) Polyols (c-1) to (c-5) and polyols (d-1) to (d-2) are mixed in the molar ratio shown in Table 1 to obtain polyol components (b-1) to (b-8). ) The phosphorus content in the polyol components (b-1) to (b-8) was measured. The results are shown in Table 1. Further, the hues of the polyol components (b-1) to (b-8) were observed. The results are shown in Table 1.
  • Example 1 To 100 parts by mass (0.05 mol) of the polyol component (b-3), 15.5 parts by mass (0.1 mol) of isophorone diisocyanate (hereinafter referred to as IPDI) is added, and dibutyltin dilaurate (hereinafter referred to as DBTDL). In the presence of 0.01 part by mass of (A), the reaction was carried out at 80 ° C. for 4 hours to obtain a urethane prepolymer.
  • IPDI isophorone diisocyanate
  • DBTDL dibutyltin dilaurate
  • urethane prepolymer 0.05 part by mass of DBTDL and 0.05 part by mass of hydroquinone monomethyl ether (hereinafter referred to as HQME) were added, and 2-hydroxyethyl acrylate (hereinafter referred to as HEA) at 50 ° C. 8.0 parts by mass (0.1 mol) was added, stirred at 60 ° C., and the reaction was carried out until the isocyanate groups disappeared while measuring the isocyanate group content by NCO titration according to JIS K1603-1. A urethane acrylate oligomer (e-1) was obtained.
  • HQME hydroquinone monomethyl ether
  • urethane acrylate oligomer e-1
  • HBMA 2-hydroxybutyl methacrylate
  • DMA n-dodecyl methacrylate
  • HCHPK 1-hydroxycyclohexyl phenyl ketone
  • Example 2 A urethane acrylate oligomer (e-2) was obtained in the same manner as in Example 1 except that the polyol (b-4) was used in place of the polyol (b-3) to prepare a photocurable resin composition.
  • Example 3 7.5 parts by weight (0.065 moles) of IPDI is added to 100 parts by weight (0.05 moles) of polyol (b-5) and reacted at 80 ° C. for 4 hours in the presence of 0.01 parts by weight of DBTDL.
  • DBTDL 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME are added to the urethane prepolymer, 5.0 parts by mass (0.03 mol) of HEA is added at 50 ° C., and the mixture is stirred at 60 ° C.
  • Example 4 A urethane acrylate oligomer (e-4) was obtained in the same manner as in Example 3 except that the polyol (b-6) was used instead of the polyol (b-5) to prepare a photocurable resin composition.
  • Example 5 To 100 parts by mass (0.05 mol) of polyol (b-6), 10 parts by mass (0.06 mol) of IPDI was added and reacted at 80 ° C. for 4 hours in the presence of 0.01 part by mass of DBTDL. A urethane prepolymer was obtained. Add 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME to the urethane prepolymer, add 5.0 parts by mass (0.02 mol) of HEA at 50 ° C, and stir at 60 ° C.
  • Example 6 10 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of HBMA, and 50 parts by mass of the urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, and 1 part of HCHPK was mixed. A part by mass was added to prepare a photocurable resin composition.
  • Example 7 80 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4 and 20 parts by mass of HBMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 8 1 part by mass of HCHPK was added to 100 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4 to prepare a photocurable resin composition.
  • Example 9 A urethane acrylate oligomer (e-6) was obtained in the same manner as in Example 4 except that the polyol (b-7) was used instead of the polyol (b-6), and the photocurable resin was obtained in the same manner as in Example 6. A composition was prepared.
  • Example 10 80 parts by mass of the urethane acrylate oligomer (e-6) obtained in Example 9 and 20 parts by mass of HBMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 11 7.0 parts by mass (0.065 mol) of hexamethylene diisocyanate (hereinafter referred to as HDI) is added to 100 parts by mass (0.05 mol) of polyol (b-6), and 0.01 parts by mass of DBTDL is added. Was reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer.
  • 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME are added to the urethane prepolymer, 5.0 parts by mass (0.03 mol) of HEA is added at 50 ° C., and the mixture is stirred at 60 ° C.
  • urethane acrylate oligomer (e-7) While measuring the isocyanate group content by NCO titration according to K1603-1, the reaction was carried out until the isocyanate group disappeared to obtain a urethane acrylate oligomer (e-7). 10 parts by mass of urethane acrylate oligomer (e-7), 40 parts by mass of HBMA, 50 parts by mass of urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, 1 part by mass of HCHPK was added, and light A curable resin composition was prepared.
  • Example 12 10 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of 2-hydroxypropyl methacrylate (hereinafter referred to as HPMA), the urethane acrylate oligomer (e-8) obtained in Example 13 ) And 1 part by mass of HCHPK were added to prepare a photocurable resin composition.
  • HPMA 2-hydroxypropyl methacrylate
  • HCHPK 2-hydroxypropyl methacrylate
  • Example 13 A urethane acrylate oligomer (e-8) was obtained in the same manner as in Example 1 except that the polyol (b-8) was used instead of the polyol (b-3). 40 parts by mass of urethane acrylate oligomer (e-8), 40 parts by mass of HPMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 14 5 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of HPMA, and 55 parts by mass of the urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, and 1 part of HCHPK was mixed. A part by mass was added to prepare a photocurable resin composition.
  • Example 15 A urethane acrylate oligomer (e-9) was obtained in the same manner as in Example 1 except that the polyol (b-1) was used instead of the polyol (b-3). 40 parts by mass of urethane acrylate oligomer (e-9), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 16 A urethane acrylate oligomer (e-10) was obtained in the same manner as in Example 1 except that the polyol (b-2) was used instead of the polyol (b-3). 40 parts by mass of urethane acrylate oligomer (e-10), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • soda lime glass As a transparent substrate, two pieces of soda lime glass having a length of 610 mm, a width of 610 mm, and a thickness of 2 mm were prepared. After sticking a double-sided adhesive tape (seal material) having a thickness of 1 mm and a width of 10 mm along the edges of the four sides of one transparent substrate, the release film on the upper surface of the double-sided adhesive tape was removed.
  • a double-sided adhesive tape adhesive material
  • An ultraviolet curable resin for sealing prepared by uniformly mixing 100 parts by mass of urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., product name “UF8001G”) and 1 part by mass of benzoin isopropyl ether (polymerization initiator) in advance
  • a coating thickness of about 0.3 mm was applied with a dispenser to form an ultraviolet curable resin layer for sealing.
  • the curable resin composition was dropped at a plurality of locations using a dispenser in a region surrounded by the double-sided adhesive tape on the surface of the transparent substrate on which the double-sided adhesive tape was applied, so that the total mass was 380 g.
  • the transparent substrate 10 in which the curable resin composition 14 was dropped in a region surrounded by the double-sided adhesive tape 12 (sealing material) was placed horizontally in the decompression chamber 26.
  • the other transparent substrate 16 is held on the upper surface plate 30 in the decompression chamber 26 by using the suction pad 32, is opposed to the transparent substrate 10 in parallel, and the distance from the transparent substrate 10 is 10 mm. .
  • the decompression chamber 26 was sealed, and the vacuum pump 28 was operated to evacuate the interior of the decompression chamber 26 to about 30 Pa. At this time, foaming of the curable resin composition 14 did not continue.
  • the upper platen 30 was lowered by the cylinder 34, and the transparent substrate 10 and the transparent substrate 16 were pressure-bonded with a pressure of 2 kPa and held for 1 minute.
  • the inside of the decompression chamber 26 was returned to atmospheric pressure in about 30 seconds, and a laminated precursor in which the transparent substrate 10 and the transparent substrate 16 were in close contact with each other through the uncured layer of the curable resin composition 14 was obtained.
  • the upper surface plate 30 was raised by the cylinder 34, and the laminated precursor adhered to the suction pad 32 of the upper surface plate 30 was peeled from the upper surface plate 30.
  • the ultraviolet curable resin 36 was cured. Thereafter, the laminated precursor was kept horizontal and allowed to stand for about 1 hour.
  • a transparent laminate (laminated glass) is obtained by curing the curable resin composition 14 by irradiating ultraviolet rays having an intensity of 1 mW / cm 2 for 10 minutes uniformly from both sides of the laminate precursor with a high-pressure mercury lamp. Obtained.
  • the evaluation results of the transparent laminate are shown in Table 3 and Table 4.
  • the transparent laminates of Examples 1 to 12 using a curable resin composition having a phosphorus content of 0.1% by mass or more had good flame retardancy and good transparency.
  • the transparent laminated bodies of Examples 13 and 14 used a curable resin composition having a phosphorus content of less than 0.1% by mass, the flame retardancy was insufficient.
  • the curable resin compositions of Examples 15 and 16 since the hydroxyl value of the polyol (a1) was high, the urethane acrylate oligomer and the monomer were not compatible. Therefore, in Examples 15 and 16, the transparent laminate was not manufactured.
  • a transparent laminate was obtained in the same manner by replacing DMA used in Examples with n-octadecyl methacrylate. Results similar to those shown in Table 2 were obtained.
  • the curable resin composition of the present invention is useful as a raw material for the adhesive resin layer of laminated glass, and the transparent laminate of the present invention includes laminated glass (windshield glass, safety glass, security glass, fire safety glass, etc.), It is useful for displays, solar cell modules and the like.
  • laminated glass windshield glass, safety glass, security glass, fire safety glass, etc.

Abstract

L'invention porte sur un stratifié transparent qui est hautement transparent et qui a un excellent caractère ignifuge et sur un procédé pour la production du stratifié. Une composition de résine durcissable (14) contenant un oligomère d'uréthane insaturé (A) qui a 2-4 groupes fonctionnels durcissables par molécule en moyenne et qui est un produit de la réaction de (A1) un ingrédient polyol qui comprend (a1) un polyol ayant 2-3 groupes hydroxy par molécule, un indice d'hydroxyle de 35-150 mg de KOH/g et un atome de phosphore dans la molécule et qui a une teneur en phosphore de 1-7 % en masse, (A2) un composé polyisocyanate et (A3) un composé hydroxy insaturé ayant le groupe fonctionnel durcissable (X) représenté ci-dessous et un groupe hydroxy est maintenue entre une paire de substrats transparents (10, 16) et est durcie pour obtenir un stratifié transparent. Le groupe fonctionnel durcissable (X) est un groupe représenté par la formule CH2=C(R)C(O)O- (dans laquelle R représente un atome d'hydrogène ou méthyle).
PCT/JP2010/062731 2009-07-30 2010-07-28 Oligomère d'uréthane insaturé, composition de résine durcissable, stratifié transparent et son procédé de production WO2011013720A1 (fr)

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WO2014076022A1 (fr) * 2012-11-14 2014-05-22 Bayer Materialscience Ag Procédé de fabrication de pièces composites

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JP6195409B2 (ja) * 2013-11-01 2017-09-13 昭和電工株式会社 不飽和ウレタン化合物、不飽和チオウレタン化合物、不飽和ウレア化合物または不飽和アミド化合物の製造方法
CN105199075B (zh) * 2014-06-30 2019-06-25 科思创德国股份有限公司 聚氨酯复合材料及其制备方法
CN107698713B (zh) * 2017-10-10 2020-07-28 重庆云天化瀚恩新材料开发有限公司 一种电能储存设备的金属表面底胶及其导电涂层组合物
JP2020196829A (ja) * 2019-06-04 2020-12-10 デクセリアルズ株式会社 光硬化性樹脂組成物及び画像表示装置の製造方法

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