WO2014017328A1 - 硬化性樹脂組成物、透明積層体およびその製造方法 - Google Patents
硬化性樹脂組成物、透明積層体およびその製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
Definitions
- the present invention relates to a curable resin composition capable of obtaining stable cured properties by having excellent storage stability, and a method for producing a transparent laminate using the composition.
- a polyurethane (meth) acrylate oligomer composition can be used for an adhesive resin layer for a transparent laminate having a pair of transparent substrates and an adhesive resin layer sandwiched between the transparent substrates.
- a curable resin composition for forming such an adhesive resin layer is obtained by reacting a polyol, isocyanate, and hydroxy (meth) acrylate with a polyurethane (meth) acrylate oligomer obtained by reacting in the presence of an organic tin compound.
- Patent Document 1 A composition to which (meth) acrylate is added is known.
- Such a curable resin composition is often stored for a certain period of time before a curing reaction is performed. In recent years, curable resin compositions used for transparent laminates are required to shorten the curing time in order to shorten the production time.
- the cured product of the curable resin composition is flexible, when used as an adhesive layer between transparent substrates, the followability with the substrate and the tearability are good.
- the curable resin composition contains a highly reactive compound such as monohydroxyalkyl (meth) acrylate, the physical properties of the resulting cured product tend to differ depending on the storage period. . In particular, when a monohydroxyalkyl acrylate having high reactivity is included, the tendency becomes remarkable.
- the present invention has excellent transparency, excellent adhesion to a transparent substrate and tear resistance, and physical properties of the cured product do not change depending on the storage period of the curable resin composition before curing.
- a curable resin composition having storage stability is provided.
- curing material layer of a curable resin composition, and its manufacturing method are provided.
- the present invention is the following [1] to [14].
- a curable resin composition comprising the following unsaturated urethane oligomer (A), the following compound (B) having one curable functional group and one hydroxyl group, the following thiol compound (D) and a photopolymerization initiator.
- Curable functional group a group represented by CH 2 ⁇ C (R) C (O) O— (wherein R represents a hydrogen atom or a methyl group).
- the polyoxyalkylene polyol (a1) has an average number of hydroxyl groups of 2 to 3, a hydroxyl value of 15 to 30 mgKOH / g, and an oxyethylene group content of 8 to 50% by mass.
- 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 according to any one of [1] to [12]
- a transparent laminate which is a cured product of the resin composition.
- a layer of the curable resin composition of any one of [1] to [12] is formed on one transparent substrate, and another layer is formed on the curable resin composition layer in a reduced-pressure atmosphere.
- curable resin composition of the present invention it is possible to obtain a curable resin composition with little change in physical properties of the cured product due to the storage period of the composition before curing.
- the curable functional group represented by CH 2 ⁇ C (R) C (O) O— (wherein R represents 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 curable resin composition of the present invention is a curable resin composition containing an unsaturated urethane oligomer (A), has good transparency, and is excellent in adhesion and tear resistance with a transparent substrate. It is suitable as a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between transparent substrates.
- Unsaturated urethane oligomer (A) Unsaturated urethane oligomer (A) is obtained by reacting polyoxyalkylene polyol (a1), polyisocyanate (a2), and compound (a3) having a curable functional group and a hydroxyl group in the presence of an organotin compound.
- the unsaturated urethane oligomer obtained by reacting the polyoxyalkylene polyol (a1) and the compound (a4) having a curable functional group and an isocyanate group in the presence of an organotin compound.
- the unsaturated urethane oligomer (A) is also referred to as an oligomer (A).
- the number of curable functional groups of the unsaturated urethane oligomer (A) is preferably 2 to 3 on average per molecule.
- the number of curable functional groups of the oligomer (A) is the number of curable functional groups of the compound (a3) or the compound (a4), the number of hydroxyl groups of the polyoxyalkylene polyol (a1), the number of isocyanate groups of the polyisocyanate (a2), etc. It can be adjusted with.
- a polyoxyalkylene polyol having an average hydroxyl number of 2 to 3 and a diisocyanate and a monohydroxyalkyl (meth) acrylate or a polyoxyalkylene polyol having an average hydroxyl number of 2 to 3 and a monoisocyanate alkyl (meth) acrylate,
- An oligomer (A) having 2 to 3 average curable functional groups can be produced.
- polyoxyalkylene diol, diisocyanate, and hydroxyalkyl (meth) acrylate having an average curable functional group of more than 1 and 1.5 or less for example, a mixture of dihydroxyalkyl (meth) acrylate and monohydroxyalkyl (meth) acrylate)
- An oligomer (A) having an average number of curable functional groups of more than 2 and 3 or less can be produced.
- polyoxyalkylene polyol (a1) is a polyoxyalkylene polyol having an average hydroxyl number of 2 to 3
- polyisocyanate (a2) is a diisocyanate
- compound (a3) is one curable functional group and one hydroxyl group.
- the proportion of the oligomer (A) is preferably 20 to 75% by mass and more preferably 40 to 60% by mass in 100% by mass of the curable resin composition.
- the ratio of the oligomer (A) is 20% by mass or more, the cured product is hardly deformed even when exposed to a high temperature. If the ratio of an oligomer (A) is 75 mass% or less, hardened
- Polyoxyalkylene polyol (a1)) The average number of hydroxyl groups of the polyoxyalkylene polyol (a1) is preferably 2-4. In order to produce the oligomer (A) having an average number of curable functional groups of 2 to 3, the average number of hydroxyl groups of the polyoxyalkylene polyol (a1) is more preferably 2 to 3.
- the polyoxyalkylene polyol (a1) is also referred to as a polyol (a1).
- the hydroxyl value of the polyol (a1) is preferably 15 to 30 mgKOH / g. If the hydroxyl value is 15 mgKOH / g or more, the strength of the cured product will be good. Moreover, since the molecular weight does not become too large, the viscosity of the polyol (a1) does not become too large, and no problem occurs in workability. When the hydroxyl value of the polyol (a1) is 30 mgKOH / g or less, high flexibility of the cured product can be maintained.
- 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 (a1) is produced by reacting an alkylene oxide with an initiator having active hydrogen in the presence of a catalyst.
- a catalyst include diethyl zinc, iron chloride, metalloporphyrin, double metal cyanide complex, cesium compound, alkali (earth) metal compound and the like, and alkali metal compound catalyst or double metal cyanide complex is preferable, double metal cyanide.
- a compound complex is particularly preferred.
- the cured product containing the oligomer (A) obtained using the polyoxyalkylene polyol having a high degree of unsaturation may have insufficient mechanical properties.
- the degree of unsaturation (USV) of the polyol (a1) is preferably 0.05 or less.
- a double metal cyanide complex catalyst in order to produce a polyol (a1) having a low hydroxyl value, it is preferable to use a double metal cyanide complex catalyst.
- a double metal cyanide complex catalyst it is difficult for a double metal cyanide complex catalyst to react with ethylene oxide alone. Therefore, when producing a block copolymer type polyoxyalkylene polyol, it is preferable to react a monoepoxide having 3 or more carbon atoms using a double metal cyanide complex catalyst and then react with ethylene oxide using another catalyst. .
- 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.
- Initiators may be used alone or in combination of two or more. When two or more are used, the number of active hydrogens in the initiator is expressed as the average number of active hydrogens.
- the average active hydrogen number of the initiator is preferably 2 to 4, more preferably 2 to 3.
- the active hydrogen means an active hydrogen atom with which an alkylene oxide can react, 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.
- the initiator is preferably a polyhydric alcohol having an average number of hydroxyl groups of 2 to 4, and more preferably a polyhydric alcohol having an average number of hydroxyl groups of 2 to 3.
- Initiators include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimerolpropane, pentaerythritol, and alkylene oxide reacted with these And a polyoxyalkylene polyol having a molecular weight lower than that of the target polyoxyalkylene polyol obtained.
- the molecular weight of the initiator is preferably 500 to 1,500, and in particular, a polyoxypropylene having a molecular weight of 500 to 1,500 obtained by reacting propylene oxide with a divalent to tetravalent polyhydric alcohol. Polyols are preferred.
- alkylene oxide examples include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide. Among these, one type may be used alone, or two or more types may be used in combination. Of the above alkylene oxides, ethylene oxide and propylene oxide are preferred. More preferably, ethylene oxide and propylene oxide are used in combination.
- the polyol (a1) is a block copolymer type polyoxyalkylene polyol obtained by reacting propylene oxide with an initiator and then with ethylene oxide, or random obtained by reacting a mixture of propylene oxide and ethylene oxide with an initiator.
- a copolymer type polyoxyalkylene polyol is preferred, and the former block copolymer type polyoxyalkylene polyol is particularly preferred.
- the average number of hydroxyl groups per molecule of the polyol (a1) is the number of active hydrogens per molecule of the initiator when there is one initiator, and when the initiator is a mixture of two types, It is an average value of the number of active hydrogens per molecule of the initiator.
- the polyol (a1) is a poly (oxypropylene / oxyethylene) polyol (hereinafter referred to as “poly (oxypropylene / oxyethylene) polyol”) having an average number of hydroxyl groups of 2 to 3, a hydroxyl value of 15 to 30 mgKOH / g, and an oxyethylene group content of 8 to 50% by mass.
- Polyol (a11)) or a mixture of this polyol (a11) and other polyols hereinafter referred to as polyol (a12)).
- the polyol (a11) is preferably contained in the polyol (a1) in an amount of 30 to 100% by mass, and more preferably 60 to 100% by mass. When the polyol (a11) is 30% by mass or more, the cured product is excellent in flexibility and transparency.
- the oxyethylene group content of the polyol (a11) is 8% by mass or more, the compatibility between the oligomer (A) and the reactive component such as the compound (B) is improved, and the transparency of the cured product is improved. . If the oxyethylene group content is 50% by mass or less, the crystallinity of the molecules (between) is relaxed and becomes a room temperature liquid, so that handling becomes easy and no problem arises in workability.
- the oxyethylene group content of the polyol can be calculated from the peak of 1 H-NMR (nuclear magnetic resonance) spectrum.
- the polyol (a12) is a polyol other than the polyol (a11).
- Examples of the polyol (a12) include a polyoxyalkylene polyol having no oxyethylene group, a polyoxyalkylene polyol having an average hydroxyl number exceeding 3 and a polyoxyalkylene polyol having a hydroxyl value exceeding 30 mgKOH / g.
- Polyisocyanate (a2) As the polyisocyanate (a2), an alicyclic polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate having an average number of isocyanate groups per molecule of 2 or more, and a modification obtained by modifying them. A polyisocyanate type
- group etc. are mentioned. Aromatic polyisocyanates having an isocyanate group bonded to an aromatic ring are preferably not used because they are likely to cause yellowing of the cured resin.
- the average number of isocyanate groups per molecule of the polyisocyanate (a2) is preferably 2 to 4, and 2 is particularly preferable. That is, as the polyisocyanate (a2), diisocyanate is preferable. Polyisocyanate (a2) may be used alone or in combination of two or more.
- polyisocyanate (a2) examples include diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, prepolymer modified products, nurate modified products, urea modified products, and carbodiimide modified products of the diisocyanate. And isophorone diisocyanate and hexamethylene diisocyanate are particularly preferable.
- the amount of the polyisocyanate (a2) relative to the polyol (a1) is preferably from 1.03 to 1.45, more preferably from 1.05 to 1.25 in terms of isocyanate index (also referred to as INDEX).
- the isocyanate index is a numerical value obtained by dividing the equivalent of the isocyanate group of the polyisocyanate by the equivalent of the hydroxyl group.
- the 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, or two or more hydroxyl groups may be present in one molecule. Good.
- a compound having one each of the curable functional group and one hydroxyl group in one molecule is preferable.
- a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 2 to 12 carbon atoms that is, a compound represented by CH 2 ⁇ C (R) C (O) O—R 4 —OH (provided that R 4 represents an alkylene group having 2 to 12 carbon atoms).
- R 4 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.
- the curable functional group is preferably an acryloyloxy group (R is a hydrogen atom).
- the compound (a3) is more preferably a hydroxyalkyl acrylate having a hydroxyalkyl having 2 to 12 carbon atoms, and particularly preferably a hydroxyalkyl acrylate having a hydroxyalkyl having 2 to 4 carbon atoms.
- the compound (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl.
- 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable, and 2-hydroxyethyl acrylate 2-hydroxypropyl acrylate is particularly preferred.
- one type may be used alone, or two or more types may be used in combination.
- the compound (a4) is a compound having a curable functional group and an isocyanate group, and two or more curable functional groups may be present in one molecule, and two or more isocyanate groups are present in one molecule. May be.
- a compound having one curable functional group and one isocyanate group in one molecule is preferable.
- the compound (a4) is particularly preferably a compound represented by CH 2 ⁇ C (R) C (O) O—R 5 —NCO (where R 5 represents an alkylene group having 1 to 6 carbon atoms).
- R is preferably a hydrogen atom.
- R 5 is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.
- one type may be used alone, or two or more types may be used in combination.
- Such a compound (a4) include 2-isocyanatoethyl methacrylate (Karenz MOI (trade name) manufactured by Showa Denko KK), 2-isocyanatoethyl acrylate (Karenz AOI (trade name): Showa Denko KK Manufactured) and the like.
- the isocyanate index is preferably 0.95 to 1.02, more preferably 0.98 to 1.00.
- the oligomer (A) can be produced by a known method from the polyol (a1) and the polyisocyanate (a2) and the compound (a3), or from the polyol (a1) and the compound (a4).
- polyol (a1) and polyisocyanate (a2) are mixed in an INDEX of 1.03 to 1.45 and reacted in the presence of an organotin compound to obtain a urethane prepolymer having an isocyanate group.
- the compound (a3) having a hydroxyl equivalent equivalent to the isocyanate group is further added, and an organic tin compound is added and reacted as necessary.
- the polyol (a1) and the compound (a4) can be produced by mixing them so that the INDEX is 0.95 to 1.02, and reacting them in the presence of an organotin compound.
- organotin compounds The organotin compound is used as a reaction catalyst for the polyol (a1), the polyisocyanate (a2), and the compound (a3), and a reaction catalyst for the polyol (a1) and the compound (a4).
- organic tin compounds include divalent tin compounds such as tin 2-ethylhexanoate, tin naphthenate, and tin stearate; dialkyltin dicarboxylates such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin monoacetate, and dibutyltin malate; Organotin carboxylates such as alkoxytin monocarboxylates, tin chelate compounds such as dialkyltin bisacetylacetonate and dialkyltin monoacetylacetonate monoalkoxide, reaction products of dialkyltin oxide and ester compounds, dialkyltin oxide and alkoxysilane Examples thereof include a reaction product of a compound and a tetravalent tin compound such as dialkyltin dialkyl sulfide.
- tin chelate compounds include dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, and dibutyltin monoacetylacetonate monoalkoxide.
- organotin carboxylates are preferable in terms of the reactivity of the urethanization reaction, and in particular, dibutyltin dilaurate and dioctyltin distearate are more preferable in terms of the reactivity and ease of handling of the urethanization reaction and hydrolysis resistance. preferable.
- the organotin compound is preferably contained in an amount of 0.0005 to 0.05% by mass, more preferably 0.010 to 0.03% by mass with respect to the oligomer (A).
- it is 0.005% by mass or more, it is preferable from the viewpoint of the reactivity of the urethanization reaction, and when it is 0.05% by mass or less, it is preferable from the viewpoint of preventing rapid gelation in the urethanization reaction.
- the compound (B) is a compound having one curable functional group and one hydroxyl group, that is, a (meth) acrylate having one hydroxyl group in one molecule.
- a (meth) acrylate having one hydroxyl group in one molecule.
- Compound (B) is a compound represented by the formula CH 2 ⁇ C (R) C (O) O—R 2 —OH (wherein R 2 represents an alkylene group).
- R 2 is preferably an alkylene group having 3 to 8 carbon atoms.
- the compound (B) is preferably an acrylate compound that is a fast-reacting compound.
- the compound (B) is effective as a component that increases the hydrophilicity of the cured product of the curable composition to improve the affinity between the cured product and the surface of the adherend, and the cured product is obtained by using the compound (B). And the adhesion between the transparent substrate and the transparent substrate are improved. In addition, the strength of the cured product is improved.
- R 2 When the carbon number of R 2 is 3 or more, the cured product has good transparency.
- the carbon number of R 2 is 8 or less, sufficient adhesion is obtained. More preferably, R 2 has 3 to 6 carbon atoms.
- a compound (B) may be used individually by 1 type, and may use 2 or more types together.
- Examples of the compound (B) include 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6 -Hydroxyhexyl acrylate and the like are mentioned, and 2-hydroxybutyl acrylate is preferred in that the resulting curable resin composition has high transparency and high reactivity.
- the compound (B) is preferably contained in an amount of 10 to 50% by mass, more preferably 25 to 45% by mass in 100% by mass of the curable resin composition. When it is 25% by mass or more, it is preferable from the viewpoint of adhesion to the substrate, and when it is 50% by mass or less, it is preferable from the viewpoint of flexibility and transparency of the cured product.
- the thiol compound (D) is a compound having one or more —SH groups.
- the group is classified into a primary thiol compound, a secondary thiol compound, and a tertiary thiol compound, depending on the number of carbon atom substituents to which the —SH group is bonded.
- the thiol compound (D) in the present invention is a thiol compound selected from the following thiol compounds (D1) and thiol compounds (D2).
- Thiol compound (D1) A primary thiol compound having a molecular weight of 70 to 420 per —SH group.
- Thiol compound (D2) secondary thiol compound having a molecular weight of 28 to 420 per —SH group.
- a thiol compound (D1) and a thiol compound (D2) may be used in combination as the thiol compound (D), and two or more of them may be used in combination as the thiol compound (D1). Two or more of them may be used in combination.
- the molecular weight per —SH group of the thiol compound (D1) is preferably from 130 to 280, more preferably from 200 to 250. When it is 70 or more, there is little change in physical properties of the cured product after storing the curable resin composition, and the physical properties of the cured product are good. When it is 420 or less, it is easy to obtain.
- the molecular weight per —SH group of the thiol compound (D2) is preferably 42 to 280, more preferably 50 to 250, and particularly preferably 70 to 250. When it is 28 or more, there is little change in physical properties of the cured product after storing the curable resin composition, and the physical properties of the cured product are good. When it is 420 or less, it is easy to obtain.
- the thiol compound (D) in the present invention is presumed to act on the organotin compound in the curable resin composition and to improve the storage stability. On the other hand, since the thiol compound also acts as a chain transfer agent, the physical properties of the cured product are improved, so that the action as a chain transfer agent is preferably as small as possible.
- the number of —SH groups contained in one molecule of the thiol compound (D) is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 4. When the number of —SH groups in one molecule is 1 or more, good storage stability is obtained, and when the number is 5 or less, commercially available products are easily available and storage stability is good. In both the primary and secondary thiol compounds (D), the smaller the molecular weight per —SH group, the easier it is to obtain a storage stability effect.
- Examples of the thiol compound (D1) include aliphatic primary thiols having 5 to 40 carbon atoms, more preferably 5 to 30 carbon atoms, and particularly preferably 5 to 20 carbon atoms.
- Examples of the thiol compound (D2) include an aliphatic secondary thiol having 3 to 40 carbon atoms and an alicyclic secondary thiol having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, 5 to 20 is particularly preferable. These compounds may have a branch in a molecular chain to which no —SH group is bonded. In both cases of the primary and secondary thiol compounds (D), the smaller the carbon number, the easier it is to obtain a storage stability effect.
- an alkanethiol and an ester of a —SH group-containing carboxylic acid and a monovalent or polyhydric alcohol are preferable.
- the —SH group-containing carboxylic acid include thioglycolic acid and 3-mercaptobutanoic acid.
- the aliphatic primary thiol 1-pentanethiol, 1-decanethiol; 1-dodecanethiol (thiocalcol 20 (trade name): manufactured by Kao Corporation), 1-hexadecanethiol, 1-octadecane Examples include thiol and 1,6-hexanediol bis (thioglycolate).
- Examples of the alicyclic secondary thiol include cyclopentane thiol and cyclohexane thiol.
- Examples of the aliphatic secondary thiol include 2-decane thiol, pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT (registered trademark)).
- PE-1 trade name: Showa Denko
- 1,4-bis (3-mercaptobutyryloxy) butane Karenz MT (registered trademark)
- BD1 trade name: Showa Denko
- the thiol compound (D) is preferably contained in an amount of 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass in 100% by mass of the curable resin composition. 0.05 mass% or more is preferable in terms of storage stability, and 3.0 mass% or less is preferable in that the photocuring reactivity and strength properties of the cured product of the curable resin composition are improved. . Moreover, since the thiol compound (D1) has a higher reactivity of the thiol group than the thiol compound (D2), it is easy to obtain the effect of storage stability with a smaller amount. The storage stability of the object may be deteriorated, and a problem due to weighing error may occur.
- the thiol compound (D2) may require a larger amount than the thiol compound (D1), but problems due to measurement errors are unlikely to occur. Therefore, when using the thiol compound (D1) as the thiol compound (D), use a relatively small amount of the above range of use, and when using the thiol compound (D2), use a relatively large amount of the range of use. It is preferable to do. Furthermore, when the thiol compound (D1) and the thiol compound (D2) are used in combination, their content ratio is not particularly limited, but the thiol compound (D1) and (D2) change their content ratio according to the purpose. Is desirable.
- the curable resin composition of this invention contains a photoinitiator, it becomes a curable resin composition which can be hardened
- the photopolymerization initiator those which are excited by irradiation with visible light or ultraviolet light (wavelength 300 to 400 nm) and are activated to promote the curing reaction are preferable.
- Benzoin ether photopolymerization initiator ⁇ -hydroxyalkylphenone light Examples thereof include a polymerization initiator and an acylphosphine oxide photopolymerization initiator.
- the photopolymerization initiator 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-hydroxyeth Si) -Phenyl] -2-hydroxy-2-methyl-1-prop
- 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 may be used individually by 1 type and may use 2 or more types together.
- the amount when the photopolymerization initiator is included is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the oligomer (A).
- 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.
- a thermal polymerization initiator By further including a thermal polymerization initiator, it becomes a photo-curing type and a thermosetting type.
- thermo-curing type By becoming a photo-curing type and a thermo-curing type, in the method for producing a transparent laminate described later, even if there is a light-shielding part on the transparent substrate and there is a part that does not easily transmit light, it is cured by heat to promote curing. Can do.
- the curable resin composition used in the method for producing the transparent laminate of the present invention preferably further contains a compound (C) having one curable functional group and an alkyl group having 8 to 22 carbon atoms.
- a compound (C) is a compound which does not have a hydroxyl group.
- an oligomer having a curable functional group other than oligomer (A) hereinafter referred to as oligomer (E)
- oligomer (E) oligomer
- compound having a curable functional group other than compound (B) and compound (C) hereinafter referred to as compound (F)).
- additive (G) an additive other than the thiol compound (D) and the polymerization initiator (hereinafter referred to as additive (G)) and the like.
- the ratio thereof is preferably 10% by mass or less with respect to the curable resin composition. The mass% or less is more preferable.
- the compound (C) is a compound represented by CH 2 ⁇ C (R) C (O) O—R 3 (wherein R 3 represents an alkyl group having 8 to 22 carbon atoms). Two or more compounds (C) may be used in combination.
- the curable resin composition contains the compound (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
- Examples of the compound (C) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate, n-dodecyl acrylate, n-octadecyl acrylate, n-behenyl acrylate, lauryl acrylate and the like, and lauryl acrylate is particularly preferable.
- the content of the compound (C) is preferably 3 to 50% by mass, and more preferably 5 to 25% by mass. If the content rate of a compound (C) is 3 mass% or more, the softness
- the curable resin composition of the present invention may contain a small amount of oligomer (E) for the purpose of adjusting the physical properties of the resulting cured product.
- Examples of the oligomer (E) include a urethane (meth) acrylate oligomer obtained using a polyol other than the polyol (a1), a poly (meth) acrylate of a polyoxyalkylene polyol, and a poly (meth) acrylate of a polyester polyol.
- the curable resin composition of the present invention may contain a small amount of a compound (F) ((meth) acrylate or the like) having one or more curable functional groups for the purpose of adjusting the physical properties of the resulting cured product.
- examples of the compound (F) include poly (meth) acrylates of polyhydric alcohols.
- the alkyl (meth) acrylate with a low carbon number of an alkyl group cannot be used as a compound (F) for the following reason.
- the compound (F) may be an alkyl (meth) acrylate having a low carbon number of an alkyl group.
- the curable resin composition When the curable resin composition is used for producing a transparent laminate by the below-described reduced pressure lamination method, it is not preferable that the curable resin composition contains a low boiling point compound.
- the curable resin composition In the reduced pressure laminating method, 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. Disappearance is severe and the composition of the curable resin composition may change significantly. In addition, it becomes difficult to maintain a reduced pressure atmosphere at a required reduced pressure level due to volatilization of volatile compounds.
- the component that tends to have a low boiling point in the curable resin composition is mainly a relatively low molecular weight compound having one curable functional group.
- Compound (B) is hydroxyalkyl (meth) acrylate, and its boiling point is sufficiently high.
- a compound (C) is alkyl (meth) acrylate, it has a boiling point higher than the carbon number of an alkyl group being large.
- Alkyl (meth) acrylates having a low number of carbon atoms in the alkyl group often have a low boiling point, and a curable resin composition containing such a low boiling point alkyl (meth) acrylate produces 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 compound 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.
- UV absorbers are used to improve the weather resistance by preventing photodegradation of the curable resin composition.
- UV absorbers such as benzotriazole, triazine, benzophenone, and benzoate Agents and the like.
- benzotriazole ultraviolet absorber examples include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4-bis (1-methyl-1-phenylethyl) -6- (2H-benzotriazole- 2-yl) phenol, 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, (2 , 2-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl)- 4,6-bis (1,1-dimethyl-propyl)
- Examples of the triazine-based ultraviolet absorber include 2- [4,6-diphenyl-1,3,5-triazin-2-yl] -5- (hexyloxy) phenol, 2- [4,6-bis (2 , 4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (isooctyloxy) -phenol.
- Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-n-octyloxybenzophenone, (2,4-dihydroxyphenyl) phenyl-methanone, and the like.
- Examples of the benzoate ultraviolet classifier include 2- [4,6-diphenyl-1,3,5-triazin-2-yl] -5- (hexyloxy) phenol.
- the light stabilizer is used for preventing light deterioration of the curable resin composition and improving the weather resistance, and examples thereof include hindered amine light stabilizers.
- hindered amine light stabilizers include the following compounds. N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -N ′-[4- [butyl (2,2,6,6-tetramethyl-4-piperidinyl) amino]- 1,3,5-triazin-2-yl] -1,6-hexanediamine, butanedioic acid 1- [2- (4-hydroxy-2,2,6,6-tetramethylpiperidino) ethyl], 2-butyl-2- (4-hydroxy-3,5-di-tert-butylbenzyl) malonic acid bis (1,2,2,6,6-pentamethylpiperidin-4-yl), decanedioic acid bis ( 1,2,2,6,6-pentamethylpiperidin-4-yl), bis (2,2,6,
- the antioxidant is used for preventing oxidation of the curable resin composition and improving weather resistance and heat resistance, and examples thereof include phenol-based and phosphorus-based antioxidants.
- examples of the phenolic antioxidant include the following compounds. Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylbis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate, N, N ′-(1,6-hexanediyl) bis [3,5-bis (1, 1-dimethylethyl) -4-hydroxybenzenepropanamide], octyl-3,5-di-tert-butyl-4-hydroxy-hydrosilicic acid, 2,4,6-tris (3 ′, 5′
- Examples of the phosphorus antioxidant include the following compounds. Triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (nonyl) Phenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl tris (dinonylphenyl) phosphite, 10 -(2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphen
- the oligomer (A) obtained using the polyol (a1) mentioned above, a compound (B), a thiol compound (D), and a photoinitiator are included. Therefore, it is possible to obtain a curable resin composition with little change in physical properties of the cured product due to the storage period before curing.
- the transparent laminate of the present invention has a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates.
- the cured resin layer is a layer made of a cured product of the curable resin composition of the present invention.
- 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 transparent panel having a high impact property and a light weight 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 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.
- the cured resin layer sandwiched between the transparent substrates is made of a cured product of the curable resin composition of the present invention, the transparency is good and the transparent It is excellent in adhesion between the substrate and the cured resin layer, as well as tear resistance and shock absorption of the cured resin layer.
- the transparent laminate of the present invention can be produced by a known production method (for example, a method in which a curable resin composition is sandwiched between a pair of transparent substrates and the curable resin composition is cured), and the pressure is reduced. It is preferable to manufacture by the manufacturing method by a lamination method.
- the reduced pressure lamination method is described in International Publication No. 08/081838 and International Publication No. 09/016943.
- 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
- First step A layer of a curable resin composition is formed on one transparent substrate, and another transparent substrate is overlaid on the layer of the curable resin composition in a reduced-pressure atmosphere to form a pair of transparent substrates.
- 2nd process The process of putting the said lamination
- the 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.
- the reduced pressure atmosphere is preferably a pressure atmosphere of 1 Pa or higher, and a pressure atmosphere of 10 Pa or higher. Is more preferable.
- the atmosphere having a higher pressure than the above-described reduced-pressure atmosphere 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.
- this manufacturing method will be described by taking as an example the case where the atmosphere having a higher pressure than the above-described 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 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 entire periphery of one surface of one transparent substrate, and the curable resin composition is supplied to the transparent substrate surface surrounded by the sealing material. These layers can be formed in an atmospheric pressure atmosphere at these stages.
- the sealed space is preferably formed as follows.
- the transparent substrate having the layer of the curable resin composition obtained above and the other transparent substrate are placed in a reduced pressure chamber to have a predetermined arrangement. That is, a transparent substrate having a layer of a curable resin composition is placed on a horizontal surface plate with the layer of the curable resin composition facing up, and a horizontal substrate attached to the tip of a cylinder capable of moving the other transparent substrate up and down. It attaches to the lower surface of a surface plate, and positions both transparent substrates 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 atmosphere inside the decompression chamber is returned to the atmospheric pressure, and the lamination precursor is taken out from the decompression chamber.
- the adhesion strength between the transparent substrate 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 allow the transparent substrate and the sealing material to adhere to each other.
- 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 in the vacuum chamber or from the vacuum chamber. After taking out, these adhesive agents and curable resin can be hardened, and the adhesive strength of a transparent substrate and a sealing material can be improved.
- the second step is a step of curing the curable resin composition under atmospheric pressure with the lamination precursor.
- the curable resin composition of the present invention is a photocurable composition containing a photopolymerization initiator
- the curable resin composition is photocured by irradiating the laminated precursor with light. Photocuring can be performed by irradiating light from a light source such as an ultraviolet lamp through a transparent substrate.
- a light source such as an ultraviolet lamp
- the curable resin composition becomes a cured resin, and the transparent laminate as described above is obtained.
- the sealing material 12 is provided over the entire periphery of one transparent substrate 10 (hereinafter simply referred to as “transparent substrate 10”), and the sealing UV curable resin 36 is provided on the sealing material 12. Is applied, and the curable resin composition 14 is supplied to the surface of the transparent substrate 10 surrounded by the sealing material 12, and is placed horizontally in the decompression chamber 26 with the layer of the curable resin composition 14 facing up. . Further, the other transparent substrate 16 (hereinafter simply referred to as “transparent substrate 16”) is held by the suction pad 32 on the upper surface plate 30 that can be moved up and down by the cylinder 34 in the decompression chamber 26, and above the transparent substrate 10. Make them face each other in parallel.
- the decompression chamber 26 is closed, and the vacuum pump 28 is operated to evacuate, so that the inside of the decompression chamber 26 has a predetermined decompressed atmosphere. Thereafter, the cylinder 34 is operated to lower the transparent substrate 16, the layer of the curable resin composition 14 is sandwiched between the transparent substrate 10 and the transparent substrate 16, and the curable resin composition 14 seals with the transparent substrate 10, the transparent substrate 16, and the seal. A laminated precursor hermetically sealed with the material 12 is formed.
- the reduced pressure chamber 26 is returned to the atmospheric pressure atmosphere, the laminated precursor is taken out from the reduced pressure chamber 26, and the curable resin composition of the laminated precursor is cured by light irradiation in the atmospheric pressure atmosphere. A transparent laminate is obtained.
- the hydroxyl value is a value determined according to JIS K1557-1 (2007 edition).
- the obtained polyoxyalkylene polyol was a poly (oxypropylene / oxyethylene) diol having an average number of hydroxyl groups of 2, a hydroxyl value of 28.7 mgKOH / g, and an oxyethylene group content of 24% by mass.
- DBTDL dibutyltin dilaurate
- DtBHQ 2,5-di-tert-butylhydroquinone
- HEA hydroxyethyl acrylate
- HCHPK 1-hydroxycyclohexyl phenyl ketone
- IRGANOX-1010 manufactured by BASF
- DtBHQ 0.04 g a polymerization inhibitor
- 1-decanethiol as 0 as a thiol compound (D) .8 g was added and mixed to prepare a curable resin composition.
- Examples 2 to 9, Comparative Examples 1 to 3 The thiol compound (D) and the addition amount of Example 1 were changed to the formulations shown in Tables 2 to 4, and curable resin compositions of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared.
- thiocalcol is a trade name of 1-dodecanethiol
- curable resin compositions of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared.
- thiocalcol is a trade name of 1-dodecanethiol
- “carenz PE-1” is a trade name of pentaerythritol tetrakis (3-mercaptobutyrate).
- Change rate (%) of storage elastic modulus (G ′) [(G ′ after oven storage at 85 ° C. ⁇ initial G ′) / initial G ′] ⁇ 100
- the change rate of the storage elastic modulus (G ′) after 2 days was evaluated as “ ⁇ ” when 30% or less, “ ⁇ ” when 30% or more and 50% or less, “ ⁇ ” when 50% or more but 80%, and “ ⁇ ” when 80% or more.
- 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 is laminated glass (windshield glass, safety glass, security glass, etc.), for display, It is useful for solar cells.
- laminated glass windshield glass, safety glass, security glass, etc.
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Abstract
Description
このような硬化性樹脂組成物は、硬化反応が行われるまでに一定期間貯蔵されることが多い。
また、近年、透明積層体に用いられる硬化性樹脂組成物は、製造時間短縮のために硬化時間を短縮することが求められている。
硬化性官能基:CH2=C(R)C(O)O-で表される基(ただし、Rは水素原子またはメチル基を表す)。
不飽和ウレタンオリゴマー(A):ポリオキシアルキレンポリオール(a1)、ポリイソシアネート(a2)、および上記硬化性官能基と水酸基とを有する化合物(a3)を有機スズ化合物の存在下反応させて得られる不飽和ウレタンオリゴマー、または、ポリオキシアルキレンポリオール(a1)および上記硬化性官能基とイソシアネート基とを有する化合物(a4)を有機スズ化合物の存在下反応させて得られる不飽和ウレタンオリゴマー。
チオール化合物(D):-SH基1個あたりの分子量が70~420である第1級チオール化合物(D1)または-SH基1個あたりの分子量が28~420である第2級チオール化合物(D2)。
[3]前記不飽和ウレタンオリゴマー(A)が、前記硬化性官能基を1分子あたり平均2~3個有する、[1]または[2]の硬化性樹脂組成物。
[4]前記ポリオキシアルキレンポリオール(a1)が、平均水酸基数が2~3、水酸基価が15~30mgKOH/g、オキシエチレン基含有量が8~50質量%である、ポリ(オキシプロピレン・オキシエチレン)ポリオールである、[1]~[3]のいずれかの硬化性樹脂組成物。
[5]前記ポリイソシアネート(a2)が、脂環族系ジイソシアネートまたは脂肪族系ジイソシアネートである、[1]~[4]のいずれかの硬化性樹脂組成物。
[6]前記化合物(a3)が、炭素数2~12のヒドロキシアルキルを有するヒドロキシアルキルアクリレートである、[1]~[5]のいずれかの硬化性樹脂組成物。
[8]前記化合物(B)が、炭素数が3~8のヒドロキシアルキルを有するモノヒドロキシアルキルアクリレートである、[1]~[7]のいずれかの硬化性樹脂組成物。
[9]前記チオール化合物(D1)が脂肪族チオール化合物である、[1]~[8]のいずれかの硬化性樹脂組成物。
[10]前記チオール化合物(D2)が、炭素数3~40の脂肪族チオール化合物または炭素数3~40の脂環族チオール化合物である、[1]~[8]のいずれかの硬化性樹脂組成物。
[11]更に、前記硬化性官能基1個と炭素数が8~22のアルキル基とを有する化合物(C)を含む、[1]~[10]のいずれかの硬化性樹脂組成物。
[12]前記硬化性樹脂組成物が、不飽和ウレタンオリゴマー(A)を20~75質量%、化合物(B)を10~50質量%およびチオール化合物(D)を0.05~3.0質量%含有する、[1]~[11]のいずれかの硬化性樹脂組成物。
[14]前記[1]~[12]のいずれかの硬化性樹脂組成物の層を1枚の透明基板上に形成し、減圧雰囲気下で前記硬化性樹脂組成物の層の上にもう1枚の透明基板を重ねて、一対の透明基板と該一対の透明基板間に密閉された前記硬化性樹脂組成物とを有する積層前駆体を製造する第1の工程と、 前記積層前駆体を、前記減圧雰囲気よりも圧力が高い雰囲気に置き、その雰囲気下で前記硬化性樹脂組成物を硬化させる第2の工程とを有することを特徴とする透明積層体の製造方法。
本発明の硬化性樹脂組成物は、不飽和ウレタンオリゴマー(A)を含む硬化性樹脂組成物であり、透明性が良好であり、透明基板との密着背および耐引き裂き性に優れるため、一対の透明基板の間に狭持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に用いられる硬化性樹脂組成物として好適なものである。
不飽和ウレタンオリゴマー(A)は、ポリオキシアルキレンポリオール(a1)、ポリイソシアネート(a2)、および硬化性官能基と水酸基とを有する化合物(a3)を有機スズ化合物の存在下で反応させて得られた不飽和ウレタンオリゴマー、または、ポリオキシアルキレンポリオール(a1)および硬化性官能基とイソシアネート基とを有する化合物(a4)を有機スズ化合物の存在下で反応させ得られた不飽和ウレタンオリゴマーである。以下、不飽和ウレタンオリゴマー(A)をオリゴマー(A)ともいう。
たとえば、平均水酸基数2~3のポリオキシアルキレンポリオールとジイソシアネートとモノヒドロキシアルキル(メタ)アクリレートとから、または、平均水酸基数2~3のポリオキシアルキレンポリオールとモノイソシアネートアルキル(メタ)アクリレートとから、平均硬化性官能基の数2~3のオリゴマー(A)を製造できる。また、ポリオキシアルキレンジオールとジイソシアネートと平均硬化性官能基の数が1を超え1.5以下のヒドロキシアルキル(メタ)アクリレート(たとえば、ジヒドロキシアルキル(メタ)アクリレートとモノヒドロキシアルキル(メタ)アクリレートの混合物)とから、平均硬化性官能基数が2を超え3以下のオリゴマー(A)を製造できる。
オリゴマー(A)としては、ポリオキシアルキレンポリオール(a1)として平均水酸基数2~3のポリオキシアルキレンポリオール、ポリイソシアネート(a2)としてジイソシアネート、化合物(a3)として硬化性官能基1個と水酸基1個を有する化合物、化合物(a4)として硬化性官能基1個とイソシアネート基1個を有する化合物、を使用して得られる不飽和ウレタンオリゴマーが好ましい。
ポリオキシアルキレンポリオール(a1)の平均水酸基数は2~4であることが好ましい。平均硬化性官能基数が2~3個であるオリゴマー(A)を製造するためには、ポリオキシアルキレンポリオール(a1)の平均水酸基数は2~3であることがより好ましい。
なお、以下、ポリオキシアルキレンポリオール(a1)をポリオール(a1)ともいう。
ポリオール(a1)の水酸基価は、JIS K1557-1(2007年版)にしたがって測定する。他のポリオールの水酸基価も同様である。
触媒としては、ジエチル亜鉛、塩化鉄、金属ポルフィリン、複合金属シアン化物錯体、セシウム化合物、アルカリ(土類)金属化合物等が挙げられ、アルカリ金属化合物触媒または複合金属シアン化物錯体が好ましく、複合金属シアン化物錯体が特に好ましい。汎用のアルカリ金属化合物触媒(水酸化カリウム等。)を用いてプロピレンオキシドを反応させて水酸基価の低いポリオキシアルキレンポリオールを得ると、プロピレンオキシドの異性化反応が起こりやすくなり、不飽和度が高くなる。不飽和度の高いポリオキシアルキレンポリオールを用いて得られるオリゴマー(A)を含む硬化物は機械的物性が不充分となるおそれがある。ポリオール(a1)の不飽和度(USV)は0.05以下が好ましい。
上記アルキレンオキシドのうち、エチレンオキシドとプロピレンオキシドが好ましい。またエチレンオキシドとプロピレンオキシドを併用することがより好ましい。
ポリオール(a12)は、ポリオール(a11)以外のポリオールである。ポリオール(a12)としては、たとえば、オキシエチレン基を有さないポリオキシアルキレンポリオール、平均水酸基数が3を超えるポリオキシアルキレンポリオール、水酸基価が30mgKOH/gを超えるポリオキシアルキレンポリオール等が挙げられる。
ポリイソシアネート(a2)としては、1分子あたりの平均イソシアネート基数が2以上の、脂環族系ポリイソシアネート、脂肪族系ポリイソシアネート、芳香環含有脂肪族系ポリイソシアネート、これらを変性して得られる変性ポリイソシアネート系等が挙げられる。芳香環に結合したイソシアネート基を有する芳香族系ポリイソシアネートは、硬化樹脂の黄変をもたらすおそれが大きいため、用いないことが好ましい。
イソシアネート指数とは、ポリイソシアネートのイソシアネート基の当量を、水酸基の当量で除した数値である。
化合物(a3)は、硬化性官能基と水酸基とを有する化合物であり、1分子中に硬化性官能基が2以上存在していてもよく、1分子中に水酸基が2以上存在していてもよい。硬化性官能基を平均2~4個有するオリゴマー(A)を製造するためには1分子中に前記硬化性官能基と水酸基をそれぞれ1つ有する化合物が好ましい。
化合物(a4)は、硬化性官能基とイソシアネート基とを有する化合物であり、1分子中に硬化性官能基が2以上存在していてもよく、1分子中にイソシアネート基が2以上存在していてもよい。硬化性官能基を平均2~4個有するオリゴマー(A)を製造するためには1分子中に硬化性官能基とイソシアネート基をそれぞれ1つ有する化合物が好ましい。
たとえば、ポリオール(a1)とポリイソシアネート(a2)とを、INDEXで1.03~1.45となるように混合し、有機スズ化合物の存在下で反応させてイソシアネート基を有するウレタンプレポリマーを得た後、イソシアネート基と当量の水酸基当量の化合物(a3)を更に加えて必要に応じて有機スズ化合物を追加して反応させる方法で製造できる。
また、ポリオール(a1)と化合物(a4)とを、INDEXが0.95~1.02となるように混合し、有機スズ化合物の存在下で反応させる方法で製造できる。
有機スズ化合物は、ポリオール(a1)とポリイソシアネート(a2)と化合物(a3)との反応触媒、およびポリオール(a1)と化合物(a4)との反応触媒として用いられる。
化合物(B)は、硬化性官能基1個と水酸基1個を有する化合物、すなわち水酸基を1分子中に1つ有する(メタ)アクリレートである。水酸基を1分子中に1個有すると、硬化物の被着材への密着性が良好でかつ、硬化物の物理的特性が良好となる。
化合物(B)は、1種を単独で用いてもよく、2種以上を併用してもよい。
チオール化合物(D)は、-SH基を1個以上有する化合物である。-SH基が結合する炭素原子の置換基の数により、第1級チオール化合物、第2級チオール化合物、第3級チオール化合物とに分類される。
チオール化合物(D1):-SH基1個あたりの分子量が70~420である第1級チオール化合物。
チオール化合物(D2):-SH基1個あたりの分子量が28~420である第2級チオール化合物。
また、チオール化合物(D)としてチオール化合物(D1)とチオール化合物(D2)を併用してもよく、更にチオール化合物(D1)としてその2種以上を併用してもよく、チオール化合物(D2)としてその2種以上を併用してもよい。
本発明におけるチオール化合物(D)は、硬化性樹脂組成物中の有機スズ化合物に作用し、貯蔵安定性が良好となると推測される。一方チオール化合物は連鎖移動剤としても作用するため、硬化物の物性が良好となるため連鎖移動剤としての作用はなるべく小さい方が好ましい。
具体的には、脂肪族第1級チオールとしては、1-ペンタンチオール、1-デカンチオール;1-ドデカンチオール(チオカルコール20(商品名):花王株式会社製)、1-ヘキサデカンチオール、1-オクタデカンチオール、1,6-ヘキサンジオールビス(チオグリコレート)が挙げられる。脂環族第2級チオールとしては、シクロペンタンチオール、シクロヘキサンチオールが挙げられ、脂肪族第2級チオールとしては、2-デカンチオール、ペンタエリスリトールテトラキス(3-メルカプトブチレート)(カレンズMT(登録商標)PE-1(商品名):昭和電工社製)、1,4-ビス(3-メルカプトブチリルオキシ)ブタン(カレンズMT(登録商標)BD1(商品名):昭和電工社製)等が挙げられる。
また、チオール化合物(D1)はチオール化合物(D2)に比べてチオール基の反応性が高いため、より少ない量で貯蔵安定性の効果が得られやすいが、多く配合し過ぎると、硬化性樹脂組成物の貯蔵安定性を悪くする場合があり、計量誤差による問題が発生するおそれがある。チオール化合物(D2)はチオール化合物(D1)よりも多い量が必要になる場合があるが、計量誤差による問題が発生しにくい。したがって、チオール化合物(D)としてチオール化合物(D1)を使用する場合は上記使用範囲のうち比較的少ない量を、チオール化合物(D2)を使用する場合は上記使用範囲のうち比較的多い量を使用することが好ましい。
更に、チオール化合物(D1)とチオール化合物(D2)を併用する場合は、それらの含有比率は特に限定はないが、目的に応じてチオール化合物(D1)と(D2)それらの含有比率を変えることが望ましい。
本発明の硬化性樹脂組成物が光重合開始剤を含むことにより、光照射により硬化しうる硬化性樹脂組成物となる。
光重合開始剤としては、可視光線または紫外線(波長300~400nm)の照射により励起され、活性化して硬化反応を促進するものが好ましく、ベンゾインエーテル系光重合開始剤、α-ヒドロキシアルキルフェノン系光重合開始剤、アシルフォスフィンオキシド系光重合開始剤等が挙げられる。
不飽和ウレタンオリゴマー(A)を含む硬化性樹脂組成物は、接着剤、コーティング剤、その他の用途に用いることができる。硬化性樹脂組成物には、用途に応じて種々の添加剤を添加できる。
また、硬化性樹脂組成物を硬化させるための硬化剤として、熱によりラジカルを発生する熱重合開始剤を更に含んでも良い。熱重合開始剤を更に含むことにより、光硬化型、かつ熱硬化型となる。光硬化型かつ熱硬化型となることにより、後述する透明積層体の製造方法において、透明基板に遮光部が設けられ光が透過しにくい部分があっても、熱硬化させて硬化を促進させることができる。
本発明の透明積層体を製造する方法に用いられる硬化性樹脂組成物は、更に硬化性官能基1個と炭素数が8~22のアルキル基とを有する化合物(C)を含むことが好ましい。なお、化合物(C)は、水酸基を有しない化合物である。場合により、オリゴマー(A)以外の硬化性官能基を有するオリゴマー(以下オリゴマー(E)という)、化合物(B)および化合物(C)以外の硬化性官能基を有する化合物(以下、化合物(F)という)、チオール化合物(D)および重合開始剤以外の添加剤(以下添加剤(G)という)等を更に含んでいてもよい。
上記オリゴマー(E)、化合物(F)または添加剤(G)が硬化性樹脂組成物に含まれる場合、その割合は、それぞれ、硬化性樹脂組成物に対して、10質量%以下が好ましく、5質量%以下がより好ましい。
化合物(C)は、CH2=C(R)C(O)O-R3で表される化合物(ただし、R3は炭素数が8~22のアルキル基を表す。)である。化合物(C)は、2種以上を併用してもよい。
硬化性樹脂組成物が化合物(C)を含む場合、化合物(C)の含有割合は、3~50質量%が好ましく、5~25質量%がより好ましい。化合物(C)の含有割合が3質量%以上であれば、硬化物の柔軟性が良好となる。
本発明の硬化性樹脂組成物は、得られる硬化物の物性を調整する目的で、オリゴマー(E)を少量含んでいてもよい。
本発明の硬化性樹脂組成物は、得られる硬化物の物性を調整する目的で、硬化性官能基を1個以上有する化合物(F)((メタ)アクリレート類等)を少量含んでいてもよい。化合物(F)としては、多価アルコールのポリ(メタ)アクリレート等が挙げられる。
また、本発明の硬化性樹脂組成物を減圧積層方法に使用する場合は、下記の理由により、化合物(F)としてアルキル基の炭素数の低いアルキル(メタ)アクリレートを使用することはできない。ただし、本発明の硬化性樹脂組成物を減圧積層方法以外の方法に使用する場合は、化合物(F)はアルキル基の炭素数の低いアルキル(メタ)アクリレートであってもよい。
一方、周辺をシールした一対の透明基板の間に液状の硬化性樹脂組成物を注入して硬化させる方法では、たとえ透明基板の間を減圧にして注入する場合であっても、注入時に減圧にさらされる硬化性樹脂組成物の表面の面積は狭く、また、減圧度もさほど高くする必要がないことから、硬化性樹脂組成物が比較的低沸点の化合物を含んでいてもその揮発が問題となることは少ない。
添加剤(G)としては、紫外線吸収剤(ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系等。)、光安定剤(ヒンダードアミン系等。)、顔料、染料、金属酸化物微粒子、フィラー等が挙げられる。
ベンゾトリアゾール系紫外線吸収剤としては、例えば、2-(2-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、2,4-ビス(1-メチル-1-フェニルエチル)-6-(2H-ベンゾトリアゾール-2-イル)フェノール、2-(5-クロロ-2-ベンゾトリアゾリル)-6-tert-ブチル-p-クレゾール、2-(2-ヒドロキシ-5-tert-オクチルフェニル)ベンゾトリアゾール、(2,2-メチレンビス〔6-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3,-テトラメチルブチル)フェノール〕、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1,1-ジメチル-プロピル)-フェノール等が挙げられる。
トリアジン系紫外線吸収剤としては、例えば、2-[4,6-ジフェニル-1,3,5-トリアジン-2-イル]-5-(ヘキシルオキシ)フェノール、2-[4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン-2-イル]-5-(イソオクチロキシ)-フェノール等が挙げられる。
ベンゾフェノン系紫外線吸収剤としては、例えば、2-ヒドロキシ-4-n-オクチルオキシベンゾフェノン、(2,4-ジヒドロキシフェニル)フェニル-メタノンなどが挙げられる。
ベンゾエート系紫外線級剤としては、例えば、2-[4,6-ジフェニル-1,3,5-トリアジン-2-イル]-5-(ヘキシルオキシ)フェノール等が挙げられる。
ヒンダードアミン系の光安定剤としては、例えば、以下の化合物が挙げられる。
N,N’-ビス(2,2,6,6-テトラメチル-4-ピペリジニル)-N’-[4-[ブチル(2,2,6,6-テトラメチル-4-ピペリジニル)アミノ]-1,3,5-トリアジン-2-イル]-1,6-ヘキサンジアミン、ブタン二酸1-[2-(4-ヒドロキシ-2,2,6,6-テトラメチルピペリジノ)エチル]、2-ブチル-2-(4-ヒドロキシ-3,5-ジ-tert-ブチルベンジル)マロン酸ビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)、デカン二酸ビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)、デカン二酸ビス(2,2,6,6-テトラメチル-4-ピペリジニル)、ブタン-1,2,3,4-テトラカルボン酸テトラキス(1,2,2,6,6-ペンタメチル-4-ピペリジニル)、1,2,3,4-ブタンテトラカルボン酸テトラキス(2,2,6,6-テトラメチルピペリジン-4-イル)、メタクリル酸1,2,2,6,6-ペンタメチル-4-ピペリジル、メタクリル酸(1,2,2,6,6-ペンタメチルピペリジン-4-イル)、メタクリル酸2,2,6,6-テトラメチル-4-ピペリジル、7-オキサ-3,20-ジアザジスピロ[5.1.11.2]ヘンエイコサン-20-プロパノン酸 2,2,4,4-テトラメチル-21-オキソ-ドデシル/テトラデシルエステル、2,2,4,4-テトラメチル-7-オキサ-3,20ジアザジスピロ[5.1.11.2]-ヘンエイコサン-21-オン、β-アラニン N-(2,2,4,4-テトラメチル-4-ピペリジニル)-ドデシル/テトラデシルエステル、2,5-ピロリジンジオン 3-ドデシル-1-(2,2,6,6-テトラメチル-4-ピペリジニル)、2,5-ピロリジンジオン N-アセチル-3-ドデシル-1-(2,2,6,6-テトラ-メチル-4-ピペリジニル)。
フェノール系酸化防止剤としては、例えば、以下の化合物が挙げられる。
ペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]、2,2’-チオジエチルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル、N,N’-(1,6-ヘキサンジイル)ビス[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシベンゼンプロパンアミド]、オクチル-3,5-ジ-tert-ブチル-4-ヒドロキシ-ヒドロ肉桂酸、2,4,6-トリス(3’,5’-ジ-tert-ブチル-4’-ヒドロキシベンジル)メシチレン、カルシウムビス[3,5-ジ(tert-ブチル)-4-ヒドロキシベンジル(エトキシ)ホスフィナート]、2,4-ビス(オクチルチオメチル)-6-メチルフェノール、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール、ビス[3-(1,1-ジメチルエチル)-4-ヒドロキシ-5-メチルベンゼンプロピオン酸]エチレンビス(オキシ-2,1-エタンジイル)、1,6-ヘキサンジオール-ビス[3(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、1,3,5-トリス[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、1,1’-イミノビス[4-(1,1,3,3-テトラメチルブチル)ベンゼン]、4-[[4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イル]アミノ]-2,6-ジ-tert-ブチルフェノール、ジエチル{[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシルフエニル] メチル}ホスホネート。
リン系酸化防止剤としては、例えば、以下の化合物が挙げられる。
トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、4,4’-ブチリデン-ビス(3-メチル-6-tert-ブチルフェニルジトリデシル)ホスファイト、サイクリックネオペンタンテトライルビス(ノニルフェニル)ホスファイト、サイクリックネオペンタンテトライルビス(ジノニルフェニル)ホスファイト、サイクリックネオペンタンテトライルトリス(ノニルフェニル)ホスファイト、サイクリックネオペンタンテトライルトリス(ジノニルフェニル)ホスファイト、10-(2,5-ジヒドロキシフェニル)-10H-9-オキサ-10-ホスファフェナントレン-10-オキシド、ジイソデシルペンタエリスリトールジホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、ビス(2,4-ジーtert-ブチルー6-メチルフェニル)=エチル=ホスファイト、ブチリデンビス[(2-tert-ブチル-5-メチル-4,1-フェニレン)オキシ]ビス(亜ホスホン酸ジトリデシル)。
本発明の透明積層体は、一対の透明基板と、該透明基板の間に挟まれた硬化樹脂の層とを有する。硬化樹脂の層は、本発明の硬化性樹脂組成物の硬化物からなる層である。
透明基板の大きさは、特に限定されないが、300mm以上、より好ましくは600mm以上の辺を少なくとも1つ有する透明基板であれば、建築用や車両用の開口部に設置する透明部材として広く利用できる。通常の用途においては、4m2以下の大きさが適当である。
硬化樹脂の層の厚さは、0.2~4.0mmが好ましい。硬化樹脂の層の厚さが0.2mm以上であれば、透明積層体の機械的強度が良好となる。
本発明の透明積層体は、公知の製造方法(たとえば、一対の透明基板の間に硬化性樹脂組成物を狭持させ、該硬化性樹脂組成物を硬化させる方法等。)によって製造でき、減圧積層方法による製造方法によって製造されることが好ましい。減圧積層方法は、国際公開第08/081838号や国際公開第09/016943号に記載されている。
第2の工程:前記積層前駆体を、前記減圧雰囲気よりも圧力が高い雰囲気に置き、その雰囲気下で前記硬化性樹脂組成物を硬化させる工程。
撹拌機および窒素導入管を備えた耐圧反応器内を用いて、亜鉛へキサシアノコバルテート-グライム錯体を触媒とし、開始剤のプロピレングリコールに、窒素雰囲気下130℃にて、プロピレンオキシドをゆっくり加えながら反応させ、触媒を失活させた後、水酸化カリウムを触媒とし、ついでエチレンオキシドを反応させた。反応容器から生成物を抜き出し、ポリオキシアルキレンポリオールを得た。得られたポリオキシアルキレンポリオールは、平均水酸基数2、水酸基価28.7mgKOH/g、オキシエチレン基含有量24質量%のポリ(オキシプロピレン・オキシエチレン)ジオールであった。
撹拌機および窒素導入管を備えた反応容器内に、ポリオールとして製造例1で得たポリ(オキシプロピレン・オキシエチレン)ジオールを460.3g、イソホロンジイソシアネート(以下、IPDIと記す。)を32.9g加え、更にジオクチルスズジステアレート(以下、DOTDSと記す。)を0.039g加えて、70℃で10時間反応させ、イソシアネート基末端ウレタンプレポリマーを得た(INDEX=1.22)。
実施例1のチオール化合物(D)および添加量を、表2~表4に記載の配合に変更し、実施例2~9、比較例1~3の硬化性樹脂組成物を調整した。
なお、表中の「チオカルコール」は、1-ドデカンチオールの商品名であり、「カレンズPE-1」は、ペンタエリスリトールテトラキス(3-メルカプトブチレート)の商品名である。
(貯蔵弾性率)
実施例1~9および比較例1~3で得られた硬化性樹脂組成物をAntonpaar社製レオメータMCR-301を用いて、HgXe(100mW/cm2)ランプにて1分硬化後の貯蔵弾性率(G’)を測定した。測定条件はサンプル厚さ0.4mm、周波数1Hz、歪1%、温度35℃とした。
実施例1~9および比較例1~3の光硬化性樹脂組成物を各々100mlの褐色バイアル瓶に約80ml取り、85℃のオーブンで1日および2日保管した後、貯蔵弾性率(G’)を測定し保管前の貯蔵弾性率からの弾性率変化を分析した。
2日後の貯蔵弾性率(G’)の変化率が30%以下を◎、30%超50%以下を○、50%超80%を△、80%超を×とした。
実施例1~9および比較例1~3の光硬化性樹脂組成物の臭気を評価者2名で臭いをかぎ、無臭と感じたものを○、不快臭がわずかにしたものを△、不快臭が強いものを×とした。
表2~表4に記載のように、実施例記載のチオール化合物(D)を添加したものは貯蔵安定性、臭気ともに比較例に比べ優れた硬化性樹脂組成物のが得られた。チオール化合物(D)を添加しない比較例1は貯蔵安定性が悪かった。-SH基あたりの分子量が本願発明の範囲外の比較例2、および-SH基あたりの炭素数が本願発明範囲外の比較例3は、初期の貯蔵弾性率G’は低くできたが、貯蔵安定性が悪かった。
なお、2012年7月23日に出願された日本特許出願2012-162536号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 下記不飽和ウレタンオリゴマー(A)、下記硬化性官能基1個と水酸基1個を有する化合物(B)、下記チオール化合物(D)および光重合開始剤を含む、硬化性樹脂組成物。
硬化性官能基:CH2=C(R)C(O)O-で表される基(ただし、Rは水素原子またはメチル基を表す)。
不飽和ウレタンオリゴマー(A):ポリオキシアルキレンポリオール(a1)、ポリイソシアネート(a2)、および上記硬化性官能基と水酸基とを有する化合物(a3)を有機スズ化合物の存在下反応させて得られる不飽和ウレタンオリゴマー、または、ポリオキシアルキレンポリオール(a1)および上記硬化性官能基とイソシアネート基とを有する化合物(a4)を有機スズ化合物の存在下反応させて得られる不飽和ウレタンオリゴマー。
チオール化合物(D):-SH基1個あたりの分子量が70~420である第1級チオール化合物(D1)または-SH基1個あたりの分子量が28~420である第2級チオール化合物(D2)。 - 前記硬化性官能基がアクリロイルオキシ基である、請求項1に記載の硬化性樹脂組成物。
- 前記不飽和ウレタンオリゴマー(A)が、前記硬化性官能基を1分子あたり平均2~3個有する、請求項1または2に記載の硬化性樹脂組成物。
- 前記ポリオキシアルキレンポリオール(a1)が、平均水酸基数が2~3、水酸基価が15~30mgKOH/g、オキシエチレン基含有量が8~50質量%である、ポリ(オキシプロピレン・オキシエチレン)ポリオールである、請求項1~3のいずれか一項に記載の硬化性樹脂組成物。
- 前記ポリイソシアネート(a2)が、脂環族系ジイソシアネートまたは脂肪族系ジイソシアネートである、請求項1~4のいずれか一項に記載の硬化性樹脂組成物。
- 前記化合物(a3)が、炭素数2~12のヒドロキシアルキルを有するヒドロキシアルキルアクリレートである、請求項1~5のいずれか一項に記載の硬化性樹脂組成物。
- 前記有機スズ化合物が有機スズカルボン酸エステルである、請求項1~6のいずれか一項に記載の硬化性樹脂組成物。
- 前記化合物(B)が、炭素数が3~8のヒドロキシアルキルを有するモノヒドロキシアルキルアクリレートである、請求項1~7のいずれか一項に記載の硬化性樹脂組成物。
- 前記チオール化合物(D1)が脂肪族チオール化合物である、請求項1~8のいずれか一項に記載の硬化性樹脂組成物。
- 前記チオール化合物(D2)が、炭素数3~40の脂肪族チオール化合物または炭素数3~40の脂環族チオール化合物である、請求項1~8のいずれか一項に記載の硬化性樹脂組成物。
- 更に、前記硬化性官能基1個と炭素数が8~22のアルキル基とを有する化合物(C)を含む、請求項1~10のいずれか一項に記載の硬化性樹脂組成物。
- 前記硬化性樹脂組成物が、不飽和ウレタンオリゴマー(A)を20~75質量%、化合物(B)を10~50質量%およびチオール化合物(D)を0.05~3.0質量%含有する、請求項1~11のいずれか一項に記載の硬化性樹脂組成物。
- 一対の透明基板と、該透明基板の間に挟まれた硬化樹脂の層とを有する透明積層体であって、
前記硬化樹脂が、請求項1~12のいずれか一項に記載の硬化性樹脂組成物の硬化物である、透明積層体。 - 請求項1~12のいずれか一項に記載の硬化性樹脂組成物の層を1枚の透明基板上に形成し、減圧雰囲気下で前記硬化性樹脂組成物の層の上にもう1枚の透明基板を重ねて、一対の透明基板と該一対の透明基板間に密閉された前記硬化性樹脂組成物とを有する積層前駆体を製造する第1の工程と、
前記積層前駆体を、前記減圧雰囲気よりも圧力が高い雰囲気に置き、その雰囲気下で前記硬化性樹脂組成物を硬化させる第2の工程と
を有することを特徴とする透明積層体の製造方法。
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JP2016176012A (ja) * | 2015-03-20 | 2016-10-06 | 日本合成化学工業株式会社 | ラジカル硬化性組成物、プラスチックシート、プラスチックシートロール及び成形物 |
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JP2022534205A (ja) * | 2019-09-09 | 2022-07-28 | エルジー・ケム・リミテッド | 硬化性組成物 |
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