CN104487470A - Curable resin composition, transparent laminate and method for producing transparent laminate - Google Patents

Curable resin composition, transparent laminate and method for producing transparent laminate Download PDF

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Publication number
CN104487470A
CN104487470A CN201380039063.1A CN201380039063A CN104487470A CN 104487470 A CN104487470 A CN 104487470A CN 201380039063 A CN201380039063 A CN 201380039063A CN 104487470 A CN104487470 A CN 104487470A
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Prior art keywords
compound
curable resin
resin composition
transparency carrier
functional group
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Chinese (zh)
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中村牧人
小黑薰
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AGC Inc
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Asahi Glass Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

Provided are: a curable resin composition which has good transparency and provides a cured resin layer exhibiting excellent tear resistance and excellent adhesion to a material to be bonded, while being free from changes in the physical characteristics of a cured product according to the storage period of an oligomer before curing and thus having excellent storage stability; and a transparent laminate. A curable resin composition which contains: (A) an unsaturated urethane oligomer which is a reaction product obtained by reacting a polyoxyalkylene polyol (a1), a polyisocyanate (a2) and an unsaturated hydroxy compound (a3) in the presence of an organic tin compound, or a reaction product obtained by reacting the polyol (a1) and an unsaturated isocyanate (a4) in the presence of an organic tin compound; (B) a compound which has one curable functional group and one hydroxyl group; (D) a thiol compound; and a photopolymerization initiator.

Description

Curable resin composition, Sparent laminate and manufacture method thereof
Technical field
The present invention relates to the manufacture method of the curable resin composition obtaining stable solidification physical property by having excellent storage stability and the Sparent laminate using said composition.
Background technology
Known urethane (methyl) origoester acrylate composition can be used for the adhesive resin layer of the Sparent laminate having a pair transparency carrier and be clipped in the adhesive resin layer between this transparency carrier.The curable resin composition for the formation of adhesive resin layer like this, adds monohydroxy (methyl) acrylate in known urethane (methyl) origoester acrylate obtained making to carry out reacting under polyvalent alcohol, isocyanic ester and the existence of hydroxyl (methyl) acrylate at organo-tin compound and the composition (patent documentation 1) obtained.
Such curable resin composition was stored certain hour mostly before being cured reaction.
In addition, in recent years, in order to shorten manufacturing time, curable resin composition used in Sparent laminate is required to shorten set time.
The cured article of above-mentioned curable resin composition is because soft, if be used as the adhesive linkage between transparency carrier, then good with the tracing ability of substrate, tearing.But, above-mentioned curable resin composition because comprise the high compound of the such reactivity of (methyl) vinylformic acid list hydroxyalkyl, so along with the difference of its storage time, there is the tendency that the physical property of the cured article of gained is different.Particularly when comprising reactive high vinylformic acid list hydroxyalkyl, this tendency becomes obvious.
Prior art document
Patent documentation
Patent documentation 1: No. 2010/134547th, International Publication
Summary of the invention
Invent technical problem to be solved
The invention provides the transparency good, with the adaptation of transparency carrier and the excellent and physical property of its cured article of resistance to tearing not with the curable resin composition with the storage stability of excellence that the storage time of the curable resin composition before solidify changes.In addition, the Sparent laminate of the resistance to tearing excellence of the layer of the adaptation between the layer that the invention provides the cured article of transparency carrier and curable resin composition and the cured article of curable resin composition and manufacture method thereof.
The technical scheme that technical solution problem adopts
The present invention is the invention of following [1] ~ [14].
[1] curable resin composition, it comprises following unsaturated urethane oligopolymer (A), has the compound (B) of 1 following solidified nature functional group and 1 hydroxyl, following sulfhydryl compound (D) and Photoepolymerizationinitiater initiater;
Solidified nature functional group: with CH 2the group that=C (R) C (O) O-represents, wherein R represents hydrogen atom or methyl;
Unsaturated urethane oligopolymer (A): the compound (a3) making polyoxyalkylene polyol (a1), polyisocyanates (a2) and have described solidified nature functional group and a hydroxyl carries out reacting and the unsaturated urethane oligopolymer obtained under the existence of organo-tin compound, or the compound (a4) making polyoxyalkylene polyol (a1) and have described solidified nature functional group and an isocyanate group carries out reacting and the unsaturated urethane oligopolymer obtained under the existence of organo-tin compound;
Sulfhydryl compound (D): the molecular weight that every 1-SH base is corresponding is uncle's sulfhydryl compound (D1) of 70 ~ 420, or molecular weight corresponding to every 1-SH base is the secondary sulfhydryl compound (D2) of 28 ~ 420.
[2] curable resin composition as described in [1], wherein above-mentioned solidified nature functional group is acryloxy.
[3] curable resin composition as described in [1] or [2], wherein, every 1 molecule of above-mentioned unsaturated urethane oligopolymer (A) on average has 2 ~ 3 above-mentioned solidified nature functional groups.
[4] curable resin composition according to any one of [1] ~ [3], wherein, poly-(oxypropyleneoxyethylene) polyvalent alcohol that above-mentioned polyoxyalkylene polyol (a1) is average hydroxyl number is 2 ~ 3, hydroxyl value is 15 ~ 30mgKOH/g, oxyethylene group content is 8 ~ 50 quality %.
[5] curable resin composition according to any one of [1] ~ [4], wherein, above-mentioned polyisocyanates (a2) is alicyclic ring same clan vulcabond or aliphatic category vulcabond.
[6] curable resin composition according to any one of [1] ~ [5], wherein, above-claimed cpd (a3) is the hydroxyalkyl acrylate of the hydroxyalkyl with carbon number 2 ~ 12.
[7] curable resin composition according to any one of [1] ~ [6], wherein, above-mentioned organo-tin compound is organotin carboxylate.
[8] curable resin composition according to any one of [1] ~ [7], wherein, above-claimed cpd (B) is the vinylformic acid list hydroxyalkyl of the hydroxyalkyl with carbon number 3 ~ 8.
[9] curable resin composition according to any one of [1] ~ [8], wherein, above-mentioned sulfhydryl compound (D1) is aliphatics sulfhydryl compound.
[10] curable resin composition according to any one of [1] ~ [8], wherein, above-mentioned sulfhydryl compound (D2) is the aliphatics sulfhydryl compound of carbon number 3 ~ 40 or the alicyclic sulfhydryl compound of carbon number 3 ~ 40.
[11] curable resin composition according to any one of [1] ~ [10], also comprises and has the compound (C) that 1 above-mentioned solidified nature functional group and carbon number are the alkyl of 8 ~ 22.
[12] curable resin composition according to any one of [1] ~ [11], wherein, above-mentioned curable resin composition contains the sulfhydryl compound (D) of the unsaturated urethane oligopolymer (A) of 20 ~ 75 quality %, the compound (B) of 10 ~ 50 quality % and 0.05 ~ 3.0 quality %.
[13] Sparent laminate, it is the Sparent laminate of the layer having a pair transparency carrier and be clipped in the cured resin between this transparency carrier, wherein, above-mentioned cured resin is the cured article of the curable resin composition according to any one of above-mentioned [1] ~ [12].
[14] manufacture method of Sparent laminate, it has following first operation and the second operation, first operation: the layer forming the curable resin composition according to any one of above-mentioned [1] ~ [12] on one piece of transparency carrier, under reduced atmosphere on the layer of above-mentioned curable resin composition another block transparency carrier overlapping, manufacture the duplexer precursor that there is a pair transparency carrier and be enclosed in the above-mentioned curable resin composition between this pair transparency carrier; Second operation: above-mentioned duplexer precursor is placed in the atmosphere higher than the pressure of above-mentioned reduced atmosphere, makes above-mentioned curable resin composition solidify under this atmosphere.
The effect of invention
According to curable resin composition of the present invention, the storage time because solidifying front composition can be obtained and the physical property of the cured article caused curable resin composition with low uncertainty.
Accompanying drawing explanation
Fig. 1 is the sectional view of the procedure represented in the manufacture of Sparent laminate.
Embodiment
In this specification sheets by CH 2=C (R) C (O) O-(wherein, R represents hydrogen atom or methyl) the solidified nature functional group that represents is acryloxy (when R is hydrogen atom), or methacryloxy (when R is methyl), is also called (methyl) acryloxy by the group represented by this formula below.Similarly, as the general name of " acrylate " and " methacrylic ester ", use " (methyl) acrylate ".
< curable resin composition >
Curable resin composition of the present invention is the curable resin composition comprising unsaturated urethane oligopolymer (A), because the transparency is good, with the adaptation of transparency carrier and resistance to tearing excellent, make the curable resin composition solidification be clamped between a pair transparency carrier manufacture the curable resin composition used in the method for Sparent laminate so be suitable as.
(unsaturated urethane oligopolymer (A))
Unsaturated urethane oligopolymer (A) is that the compound (a3) making polyoxyalkylene polyol (a1), polyisocyanates (a2) and have solidified nature functional group and a hydroxyl carries out reacting and the unsaturated urethane oligopolymer obtained under the existence of organo-tin compound, or the compound (a4) making polyoxyalkylene polyol (a1) and have solidified nature functional group and an isocyanate group carries out reacting and the unsaturated urethane oligopolymer obtained under the existence of organo-tin compound.Below, also unsaturated urethane oligopolymer (A) is called oligopolymer (A).
The quantity of the solidified nature functional group of unsaturated urethane oligopolymer (A) is better average out to 2 ~ 3 in every 1 molecule.The quantity of the solidified nature functional group of oligopolymer (A) adjusts by the quantity of the solidified nature functional group of compound (a3) and compound (a4), the hydroxyl value of polyoxyalkylene polyol (a1), the isocyanic ester radix etc. of polyisocyanates (a2).
Such as, by by the polyoxyalkylene polyol of average hydroxyl number 2 ~ 3 and vulcabond and (methyl) vinylformic acid list hydroxyalkyl, or manufacture by the polyoxyalkylene polyol of average hydroxyl number 2 ~ 3 and monoisocyanates alkyl (methyl) acrylate the oligopolymer (A) that average curing property functional group number is 2 ~ 3.In addition, by being manufactured the oligopolymer (A) of average curing property functional group number more than 2 and below 3 by polyoxyalkylene diols and vulcabond and average solidified nature functional group number (methyl) hydroxyalkyl acrylate (mixture of such as (methyl) vinylformic acid two hydroxyalkyl and (methyl) vinylformic acid list hydroxyalkyl) more than 1 and below 1.5.
As oligopolymer (A), better unsaturated urethane oligopolymer, its by use the polyoxyalkylene polyol of average hydroxyl number 2 ~ 3 as polyoxyalkylene polyol (a1), use vulcabond as polyisocyanates (a2), use there is 1 solidified nature functional group and 1 hydroxyl compound as compound (a3), use the compound with 1 solidified nature functional group and 1 isocyanate group to obtain as compound (a4).
The ratio of oligopolymer (A) is better 20 ~ 75 quality % in curable resin composition 100 quality %, more preferably 40 ~ 60 quality %.If the ratio of oligopolymer (A) is more than 20 quality %, even if cured article is not yielding yet under being then exposed to high temperature.If the ratio of oligopolymer (A) is at below 75 quality %, then cured article not easily becomes fragile.
(polyoxyalkylene polyol (a1))
The average hydroxyl number of polyoxyalkylene polyol (a1) is better 2 ~ 4.In order to manufacture the oligopolymer (A) that average curing property functional group number is 2 ~ 3, the average hydroxyl number of polyoxyalkylene polyol (a1) is more preferably 2 ~ 3.
Below, by polyoxyalkylene polyol (a1) also referred to as polyvalent alcohol (a1).
The hydroxyl value of polyvalent alcohol (a1) is better 15 ~ 30mgKOH/g.If hydroxyl value is at more than 15mgKOH/g, then the intensity of cured article is good.In addition, because molecular weight can not become excessive, therefore the viscosity of polyvalent alcohol (a1) also can not become excessive, thus can not produce the problem in operability.If the hydroxyl value of polyvalent alcohol (a1) is at below 30mgKOH/g, then cured article can maintain higher flexibility.
The hydroxyl value of polyvalent alcohol (a1) measures according to JIS K1557-1 (version in 2007).The hydroxyl value of other polyvalent alcohol too.
Polyvalent alcohol (a1), by the presence of a catalyst, makes alkylene oxide manufacture with the initiator for reaction with active hydrogen.
As catalyzer, zinc ethyl, iron(ic) chloride, metalloporphyrin, composition metal cyanide complex, Cesium compound, alkali (alkaline earth) metallic compound etc. can be exemplified, better alkali metal compound catalyzer or composition metal cyanide complex, particularly preferably composition metal cyanide complex.If use general alkali metal compound catalyzer (potassium hydroxide etc.) make propylene oxide reaction and obtain the low polyoxyalkylene polyol of hydroxyl value, then the isomerization reaction of easy initial ring Ethylene Oxide, degree of unsaturation uprises.The polyoxyalkylene polyol high containing useful degree of unsaturation and the mechanical properties of the cured article of the oligopolymer (A) obtained likely becomes not enough.The degree of unsaturation (USV) of polyvalent alcohol (a1) preferably less than 0.05.
Thus, in order to manufacture the low polyvalent alcohol of hydroxyl value (a1), be better use composite metal cyanide complex catalyst.On the other hand, composite metal cyanide complex catalyst is difficult to oxyethane is reacted separately.Thus, when manufacturing the polyoxyalkylene polyol of segmented copolymer type, being better after making carbon number be the monoepoxide reaction of more than 3 with composite metal cyanide complex catalyst, then making reacting ethylene oxide with other catalyzer.
As composition metal cyanide complex, be better take zinc hexacyanocobaltate as the complex compound of main component, particularly preferably the ether of zinc hexacyanocobaltate and/or alcohol complex.As ether and/or the alcohol complex of zinc hexacyanocobaltate, the complex compound recorded in Japanese Patent examined patent publication 46-27250 publication can be exemplified.As ether, be better glycol dimethyl ether (glyme), diethylene glycol dimethyl ether etc., in the operational ease when manufacturing complex compound, spy is glyme well.As alcohol, the trimethyl carbinol, tertiary butyl cellosolve etc. can be exemplified.
Initiator can be used alone a kind, also can two or more also use.When using two or more, the active hydrogen number of initiator can be used as average activity hydrogen number and represents.The average activity hydrogen number of initiator is better 2 ~ 4, is more preferably 2 ~ 3.Active hydrogen refer to the hydrogen atom of hydroxyl, amino hydrogen atom etc. can with the active hydrogen atom of alkylene oxide reaction.As active hydrogen, it is better the hydrogen atom of hydroxyl.Thus, as initiator, to be better average hydroxyl number be 2 ~ 4 polyvalent alcohol, be more preferably the polyvalent alcohol that average hydroxyl number is 2 ~ 3.As initiator, ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1 can be exemplified, 4-butyleneglycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, alkylene oxide is reacted with them and the ratio obtained as the low polyoxyalkylene polyol etc. of the molecular weight of the polyoxyalkylene polyol of target.When using composite metal cyanide complex catalyst, the molecular weight of initiator preferably 500 ~ 1500, spy is well the molecular weight obtained by the polyol reaction of propylene oxide and 2 ~ 4 yuan is the polyoxypropylene polyol of 500 ~ 1500.
As alkylene oxide, oxyethane, propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide rings, Styrene oxide 98min. etc. can be exemplified.Can be used alone a kind in them, also can two or more also use.
In above-mentioned alkylene oxide, be better oxyethane and propylene oxide.In addition, be more preferably oxyethane and propylene oxide and use.
As polyvalent alcohol (a1), be better make propylene oxide and initiator for reaction after make oxyethane carry out reacting again and the polyoxyalkylene polyol of the segmented copolymer type obtained or make the mixture of propylene oxide and oxyethane and initiator for reaction and the polyoxyalkylene polyol of the atactic copolymer type obtained, spy is well the polyoxyalkylene polyol of the former segmented copolymer type.
When initiator is a kind, the average hydroxyl number of the polyvalent alcohol (a1) of every 1 molecule is the active hydrogen number of the initiator of every 1 molecule; When initiator is the mixture of 2 kinds, the average hydroxyl number of the polyvalent alcohol (a1) of every 1 molecule is this mean value as the active hydrogen number of the initiator of mixture of every 1 molecule.
As polyvalent alcohol (a1), be better average hydroxyl number be 2 ~ 3, hydroxyl value be 15 ~ 30mgKOH/g, poly-(oxypropyleneoxyethylene) polyvalent alcohol (hereinafter referred to as polyvalent alcohol (a11)) that oxyethylene group content is 8 ~ 50 quality %, or the mixture of this polyvalent alcohol (a11) and polyvalent alcohol (hereinafter referred to as polyvalent alcohol (a12)) in addition.
Polyvalent alcohol (a11) better containing 30 ~ 100 quality % in polyvalent alcohol (a1), is more preferably 60 ~ 100 quality %.If polyvalent alcohol (a11) is at more than 30 quality %, then flexibility, the transparency excellence of cured article.
If the oxyethylene group content of polyvalent alcohol (a11) is at more than 8 quality %, then oligopolymer (A) improves with the intermiscibility of the reactive ingredients of compound (B) etc., and the transparency of cured article is good.If oxyethylene group content is at below 50 quality %, then become normal temperature solid owing to having relaxed the crystallinity of molecule (), therefore operation becomes easy and problem that is that can not produce in operability.
The oxyethylene group content of polyvalent alcohol can be passed through 1the peak that H-NMR (nucleus magnetic resonance) composes calculates.
(polyvalent alcohol (a12))
Polyvalent alcohol (a12) is the polyvalent alcohol beyond polyvalent alcohol (a11).As polyvalent alcohol (a12), can exemplify such as not there is oxyethylene group polyoxyalkylene polyol, the polyoxyalkylene polyol of average hydroxyl number more than 3, hydroxyl value is more than the polyoxyalkylene polyol etc. of 30mgKOH/g.
(polyisocyanates (a2))
As polyisocyanates (a2), the average isocyanate number of ester groups that can exemplify every 1 molecule is the alicyclic ring same clan polyisocyanates of more than 2, aliphatic category polyisocyanates, the aliphatic category polyisocyanates containing aromatic nucleus, the modified polyisocyanate class etc. that their modifications obtained.Because the fragrant same clan polyisocyanates being combined with isocyanate group on aromatic nucleus causes the xanthochromia of cured resin possibly, therefore preferably do not use.
The average isocyanate number of ester groups of the polyisocyanates (a2) of every 1 molecule preferably 2 ~ 4, particularly preferably 2.That is, as polyisocyanates (a2), preferably vulcabond.Polyisocyanates (a2) can be used alone a kind, also can two or more also use.
As the object lesson of polyisocyanates (a2), isophorone diisocyanate, dicyclohexyl methane diisocyanate, 1 can be exemplified, the vulcabond such as hexamethylene-diisocyanate, xylylene diisocyanate, the prepolymer modification body of this vulcabond, urea acid esters (ヌ レ ー ト) modification body, urea modification body, carbodiimide modified body etc., particularly preferably isophorone diisocyanate, hexamethylene diisocyanate.
It is 1.03 ~ 1.45 that polyisocyanates (a2) is haggled over isocyanate index (also referred to as INDEX) relative to the amount of polyvalent alcohol (a1), is more preferably 1.05 ~ 1.25.
Isocyanate index refers to the numerical value obtained divided by the equivalent of hydroxyl by the equivalent of the isocyanate group of polyisocyanates.
(compound (a3))
Compound (a3) is the compound with solidified nature functional group and hydroxyl, can there is the solidified nature functional group of more than 2 in 1 molecule, also can there is the hydroxyl of more than 2 in 1 molecule.In order to prepare the oligopolymer (A) with average 2 ~ 4 solidified nature functional groups, it is better the compound respectively in 1 molecule with 1 above-mentioned solidified nature functional group and 1 hydroxyl.
As compound (a3), be better (methyl) hydroxyalkyl acrylate of the hydroxyalkyl with carbon number 2 ~ 12, namely with CH 2=C (R) C (O) O-R 4compound (wherein, the R that-OH represents 4represent the alkylidene group of carbon number 2 ~ 12).R 4to be better carbon number be 2 ~ 8 alkylidene group, be more preferably the alkylidene group that carbon number is 2 ~ 4.In order to obtain reactive high oligopolymer (A), be better solidified nature functional group be acryloxy (R is hydrogen atom).Thus, as compound (a3), be more preferably the hydroxyalkyl acrylate of the hydroxyalkyl with carbon number 2 ~ 12, particularly preferably there is the hydroxyalkyl acrylate of the hydroxyalkyl of carbon number 2 ~ 4.
As the object lesson of compound (a3), (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxy propyl ester, (methyl) vinylformic acid-2-hydroxybutyl, (methyl) vinylformic acid-4-hydroxybutyl, pentanediol list (methyl) acrylate, hexylene glycol list (methyl) acrylate etc. can be exemplified, better (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, particularly preferably 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate.Compound (a3) can be used alone a kind, also can two or more also use.
(compound (a4))
Compound (a4) is the compound with solidified nature functional group and isocyanate group, can there is the solidified nature functional group of more than 2 in 1 molecule, also can there is the isocyanate group of more than 2 in 1 molecule.In order to prepare the oligopolymer (A) with average 2 ~ 4 solidified nature functional groups, it is better the compound respectively in 1 molecule with 1 solidified nature functional group and 1 isocyanate group.
As compound (a4), spy is with CH well 2=C (R) C (O) O-R 5compound (wherein, the R that-NCO represents 5represent the alkylidene group of carbon number 1 ~ 6).In order to obtain reactive high oligopolymer (A), R is better hydrogen atom.In addition, R 5to be better carbon number be 1 ~ 4 alkylidene group, be more preferably the alkylidene group that carbon number is 1 or 2.Compound (a4) can be used alone a kind, also can two or more also use.
As the concrete example of such compound (a4), can exemplified by methyl vinylformic acid 2-isocyanato ethyl (カ レ Application ズ MOI (trade(brand)name): Showa Denko K. K (Showa Electricity work society) makes), vinylformic acid 2-isocyanato ethyl (カ レ Application ズ AOI (trade(brand)name): Showa Denko K. K's system) etc.
When polyvalent alcohol (a1) and compound (a4) are reacted, haggling over isocyanate index is 0.95 ~ 1.02, is more preferably 0.98 ~ 1.00.
Oligopolymer (A), by known method, is manufactured by polyvalent alcohol (a1) and polyisocyanates (a2) and compound (a3), or by polyvalent alcohol (a1) and compound (a4) manufacture.
In addition, manufacture by following method: polyvalent alcohol (a1) and polyisocyanates (a2) are mixed according to the condition that INDEX is 1.03 ~ 1.45, it is made to carry out reacting under the existence of organo-tin compound and after obtaining having the carbamate prepolymer of isocyanate group, the compound (a3) that further interpolation isocyanate group equivalent is identical with hydroxyl equivalent, is added with machine tin compound as required and makes it react.
In addition, can, by polyvalent alcohol (a1) and compound (a4) being mixed according to the condition that INDEX is 0.95 ~ 1.02, its method of carrying out reacting under the existence of organo-tin compound be manufactured.
(organo-tin compound)
Organo-tin compound can be used as the catalysts of polyvalent alcohol (a1) and polyisocyanates (a2) and compound (a3) and the catalysts of polyvalent alcohol (a1) and compound (a4).
As organo-tin compound, can exemplify: the divalent tin compounds such as 2 ethyl hexanoic acid tin, naphthenic acid tin, stearic acid tin; The dialkyltin dicarboxylates such as dibutyl tin dilaurate, oxalic acid two fourth tin, single acetic acid two fourth tin, dibutyltin maleate or the such organotin-carboxylate of dialkoxy tin monocarboxylate, bis-acetylacetonate closes dialkyl tin, single acetyl acetone list alkanol closes the tin chelate compounds such as dialkyl tin, the reaction product of dialkyl tin oxide and ester cpds, the reaction product of dialkyl tin oxide and alkoxysilane compound containing trialkylsilyl group in molecular structure, the 4 valency tin compounds such as dialkyl tin dialkyl sulfide.
As tin chelate compound, can exemplify that bis-acetylacetonate closes two fourth tin, diacetyl acetate ethyl ester closes dibutyl tin, single acetyl acetone list alkanol and closes two fourth tin etc.
In these compounds, urethane reaction reactive in, better organotin-carboxylate, wherein the reactivity of urethane reaction and the easness of operation, hydrolytic resistance in, be more preferably dibutyl tin dilaurate, distearyl acid two fourth tin.
Organo-tin compound be better relative to oligopolymer (A) containing 0.0005 ~ 0.05 quality %, be more preferably 0.010 ~ 0.03 quality %.If at more than 0.005 quality %, then urethane reaction reactive in be desirable, if at below 0.05 quality %, then prevent urethane react in sharply gelation in be desirable.
(compound (B))
Compound (B) is the compound with 1 solidified nature functional group and 1 hydroxyl, namely has (methyl) acrylate of 1 hydroxyl in 1 molecule.If have 1 hydroxyl in 1 molecule, then cured article is to good by the adaptation of sticky material, and the physical property of cured article is good.
Compound (B) is with formula CH 2=C (R) C (O) O-R 2compound (wherein, the R that-OH represents 2represent alkylidene group).R 2it is better the alkylidene group of carbon number 3 ~ 8.Compound (B) is better the acrylic compound as reacting compound faster.Compound (B) as improve solidification compound cured article wetting ability, improve cured article and effective by the composition of the affinity between the surface of sticky material, improve adaptation between cured article and transparency carrier by using compound (B).In addition, the intensity of cured article is also improved.
If R 2carbon number more than 3, then the transparency of cured article is good.In addition, if R 2carbon number be less than 8, then can obtain sufficient adaptation.R 2carbon number be more preferably 3 ~ 6.
Compound (B) can be used alone one, also can be two or more and use.
As compound (B), can exemplified by methyl vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxybutyl, methacrylic acid 4-hydroxybutyl, the own ester of methacrylic acid 6-hydroxyl, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 2-hydroxybutyl, vinylformic acid 4-hydroxybutyl, the own ester of vinylformic acid 6-hydroxyl etc., in high in the transparency of the curable resin composition of gained, reactive high, it is better vinylformic acid 2-hydroxybutyl.
Compound (B) better containing 10 ~ 50 quality % in 100 quality % of curable resin composition, is more preferably 25 ~ 45 quality %.If at more than 25 quality %, be then desirable in the adaptation to substrate, if at below 50 quality %, then cured article flexibility, the transparency in be desirable.
(sulfhydryl compound (D))
Sulfhydryl compound (D) has the compound of more than 1-SH base.According to the substituting group quantity of the carbon atom that-SH base combines, uncle sulfhydryl compound, secondary sulfhydryl compound, tertiary sulfhydryl compound can be categorized as.
Sulfhydryl compound (D) in the present invention is the sulfhydryl compound being selected from following sulfhydryl compound (D1) and sulfhydryl compound (D2).
Sulfhydryl compound (D1): the molecular weight that every 1-SH base is corresponding is uncle's sulfhydryl compound of 70 ~ 420.
Sulfhydryl compound (D2): the molecular weight that every 1-SH base is corresponding is the secondary sulfhydryl compound of 28 ~ 420.
In addition, as sulfhydryl compound (D), can be used together sulfhydryl compound (D1) and sulfhydryl compound (D2), in addition, can be used together its two or more as sulfhydryl compound (D1), can be used together its two or more as sulfhydryl compound (D2).
The molecular weight that every 1-SH base of sulfhydryl compound (D1) is corresponding is better 130 ~ 280, is more preferably 200 ~ 250.If more than 70, then the physical property of the cured article after being preserved by curable resin composition is with low uncertainty and the physical property of cured article is good.If below 420, then easily obtain.
The molecular weight that every 1-SH base of sulfhydryl compound (D2) is corresponding is better 42 ~ 280, and be more preferably 50 ~ 250, spy is 70 ~ 250 well.If more than 28, then the physical property of the cured article after being preserved by curable resin composition is with low uncertainty and the physical property of cured article is good.If below 420, then easily obtain.
Can infer that the sulfhydryl compound (D) in the present invention is had an effect with the organo-tin compound in curable resin composition, storage stability becomes good.On the other hand, sulfhydryl compound also plays a role as chain-transfer agent, and the physical property of cured article becomes good, and therefore, the effect as chain-transfer agent is preferably little as far as possible.
-SH radix contained in the sulfhydryl compound (D) of 1 molecule is not particularly limited, is better 1 ~ 5, is more preferably 1 ~ 4.If-SH the base in 1 molecule is more than 1, then can obtain good storage stability, if below 5, then easily obtain commercially available product, storage stability is good.Sulfhydryl compound (D) is uncle's sulfhydryl compound, in secondary sulfhydryl compound any one when, the molecular weight that every 1-SH base is corresponding is less, more easily obtains the effect of storage stability.
As sulfhydryl compound (D1), can exemplify the aliphatic primary mercaptans that carbon number is 5 ~ 40, carbon number is better 5 ~ 30, and spy is 5 ~ 20 well.As sulfhydryl compound (D2), can exemplify carbon number be 3 ~ 40 aliphatic secondary mercaptan and carbon number be 3 ~ 40 alicyclic secondary mercaptan, carbon number is more preferably 3 ~ 30, and spy is 5 ~ 20 well.These compounds can have side chain on the molecular chain not having combination-SH base.Sulfhydryl compound (D) is uncle's sulfhydryl compound, in secondary sulfhydryl compound any one when, carbon number is less, more easily obtains the effect of storage stability.
As aliphatic primary mercaptans compound or aliphatic secondary mercaptan compound, it is better alkanethiol and containing the carboxylic acid of-SH base and the ester of monohydroxy-alcohol ~ polyvalent alcohol.As the carboxylic acid containing-SH base, Thiovanic acid and 3-mercaptobutyric acid etc. can be exemplified.
Specifically, as aliphatic primary mercaptans, 1-pentan-thiol, 1-decyl mercaptan can be exemplified; 1-Dodecyl Mercaptan (チ オ カ Le コ mono-Le 20 (trade(brand)name): Kao Corp's system), two (Thiovanic acid) ester of 1-16 mercaptan, 1-stearylmercaptan, 1,6-hexylene glycol.As alicyclic secondary mercaptan, cyclopentyl mercaptan, cyclohexylmercaptan can be exemplified, as aliphatic secondary mercaptan, 2-decyl mercaptan, four (3-mercaptobutyric acid) pentaerythritol ester (カ レ Application ズ MT (registered trademark) PE-1 (trade(brand)name): Showa Denko K. K's system), Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane (カ レ Application ズ MT (registered trademark) BD1 (trade(brand)name): Showa Denko K. K's system) etc. can be exemplified.
Sulfhydryl compound (D) better containing 0.05 ~ 3.0 quality % in 100 quality % of curable resin composition, is more preferably 0.1 ~ 2.0 quality %.If at more than 0.05 quality %, be then desirable in storage stability, if at below 3.0 quality %, then the intensity physical property of the cured article of photocuring reaction and curable resin composition good in be desirable.
In addition, sulfhydryl compound (D1) is compared with sulfhydryl compound (D2), the reactivity of sulfydryl is higher, therefore the easy effect obtaining storage stability with less amount, if but it is blended many, then the storage stability of curable resin composition is likely deteriorated, and the problem caused because of error in dipping likely occurs.Sulfhydryl compound (D2) needs more to measure than sulfhydryl compound (D1) sometimes, but the problem that causes because of error in dipping is less likely to occur.Therefore, in use sulfhydryl compound (D1) as the less amount better adopted time sulfhydryl compound (D) in above-mentioned use range, in use sulfhydryl compound (D2) as the more amount better adopted time sulfhydryl compound (D) in above-mentioned use range.
In addition, when also with sulfhydryl compound (D1) and sulfhydryl compound (D2), being not particularly limited containing ratio them, but it is desirable to change sulfhydryl compound (D1) and (D2) according to object contain ratio.
(Photoepolymerizationinitiater initiater)
Curable resin composition of the present invention, by containing Photoepolymerizationinitiater initiater, forms the curable resin composition solidified by rayed.
As Photoepolymerizationinitiater initiater; be better be excited by the irradiation of visible ray or ultraviolet (wavelength 300 ~ 400nm), activate and promote the initiator of curing reaction, benzoin ethers Photoepolymerizationinitiater initiater, alpha-hydroxyalkyl benzophenone class Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater etc. can be exemplified.
As the object lesson of Photoepolymerizationinitiater initiater, benzophenone can be exemplified, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, 4,4 '-diaminobenzophenone, methyl phenyl ketone, 3-methyl acetophenone, benzoyl, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide etc., preferably 1-hydroxycyclohexylphenylketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, two (2, 4, 6-trimethylbenzoyl)-phenyl phosphine oxide etc., even if consider from the angle also curable resin composition fully can solidified when trace adds, particularly preferably two (2, 4,6-trimethylbenzoyl) the acylphosphine oxide class Photoepolymerizationinitiater initiater such as-phenyl phosphine oxide.Photoepolymerizationinitiater initiater can be used alone a kind, also can two or more also use.
When containing photopolymerization initiator, its content relative to oligopolymer (A) preferably 0.01 ~ 10 mass parts of 100 mass parts, more preferably 0.1 ~ 2.5 mass parts.
(other compositions)
Curable resin composition containing unsaturated urethane oligopolymer (A) may be used for caking agent, coating agent and other purposes.Different according to purposes, various additive can be added in curable resin composition.
In addition, as the solidifying agent that curable resin composition can be solidified, the thermal polymerization of free radical can also be produced containing utilizing heat.By further containing thermal polymerization, become light-cured type and thermohardening type.By becoming light-cured type and thermohardening type, in the manufacture method of Sparent laminate described later, even if arranging light shielding part at transparency carrier and there is the not meable part of light, also can make its thermofixation and promoting solidification.
(being suitable for the curable resin composition manufacturing Sparent laminate)
Manufacture curable resin composition used in the method for Sparent laminate of the present invention better also containing the compound (C) of alkyl with 1 solidified nature functional group and carbon number 8 ~ 22.In addition, compound (C) is the compound without hydroxyl.According to circumstances, the additive (hereinafter referred to as additive (G)) etc. beyond compound (hereinafter referred to as compound (F)), sulfhydryl compound (D) and the coincidence initiator with solidified nature functional group beyond oligopolymer (hereinafter referred to as oligopolymer (E)), compound (B) and the compound (C) with solidified nature functional group beyond oligopolymer (A) can also be contained.
Comprise in curable resin composition above-mentioned oligopolymer (E), compound (F) or additive (G) when, its ratio is better be below 10 quality % relative to curable resin composition respectively, is more preferably below 5 quality %.
(compound (C))
Compound (C) is with CH 2=C (R) C (O) O-R 3compound (wherein, the R represented 3represent that carbon number is the alkyl of 8 ~ 22).Compound (C) can two or more also be used.
Curable resin composition, by containing compound (C), makes the Young's modulus of cured article reduce, easily improves resistance to tearing.In addition, if the carbon number of alkyl is more than 8, then volatility is little, and the second-order transition temperature of cured article can be made to reduce.If the carbon number of alkyl is below 22, then easily obtain.
As compound (C), can exemplified by methyl vinylformic acid dodecyl ester, methacrylic acid Octadecane base ester, methacrylic acid n-docosane base ester, vinylformic acid dodecyl ester, vinylformic acid Octadecane base ester, vinylformic acid n-docosane base ester, lauryl alcohol ester etc., particularly preferably lauryl alcohol ester.
When curable resin composition contains compound (C), compound (C) containing proportional be better 3 ~ 50 quality %, be more preferably 5 ~ 25 quality %.If containing of compound (C) is proportional at more than 3 quality %, then the flexibility of cured article is good.
(oligopolymer (E))
For the purpose of the physical property adjusting the cured article obtained, curable resin composition of the present invention also can comprise a small amount of oligopolymer (E).
As oligopolymer (E), can exemplify and use the polyvalent alcohol beyond polyvalent alcohol (a1) and carbamate (methyl) origoester acrylate, poly-(methyl) acrylate of polyoxyalkylene polyol, poly-(methyl) acrylate etc. of polyester polyol of obtaining.
(compound (F))
For the purpose of the physical property adjusting the cured article obtained, curable resin composition of the present invention can comprise a small amount of compound (F) ((methyl) esters of acrylic acid etc.) with the solidified nature functional group of more than 1.As compound (F), poly-(methyl) acrylate etc. of polyvalent alcohol can be exemplified.
In addition, when being used for reducing pressure laminating method by curable resin composition of the present invention, due to following reason, alkyl (methyl) acrylate that the carbon number of alkyl is few can not be used as compound (F).But during method beyond the laminating method that is used for by curable resin composition of the present invention reducing pressure, compound (F) can be alkyl (methyl) acrylate that the carbon number of alkyl is few.
Curable resin composition by decompression laminating method described later for the manufacture of Sparent laminate time, curable resin composition should not comprise lower boiling compound.In decompression layered manner, due to curable resin composition except the edge section of transparency carrier almost all sidedly with launch state be exposed to decompression state under, so when curable resin composition comprises lower boiling compound, the dissipation caused because of its volatilization is relatively more violent, likely makes the composition of curable resin composition that larger change occurs.And, be difficult to maintain the reduced atmosphere of necessary vacuum tightness due to the volatilization of volatile compound.
On the other hand, liquid curable resin composition is injected and the method making it solidify between a pair transparent glass substrate to peripheral sealing, even inject after decompression between transparency carrier, the area being exposed to the surface of the curable resin composition under decompression state when injecting is also less, and it is very high owing to there is no need vacuum tightness to rise to, even if so curable resin composition comprises the lower compound of boiling point, the problem of its volatilization also seldom occurs.
The lower boiling composition that easily becomes in curable resin composition mainly has the lower compound of the molecular weight of 1 solidified nature functional group.Compound (B) is (methyl) hydroxyalkyl acrylate, and its boiling point is enough high.In addition, compound (C), even (methyl) alkyl acrylate, also has high boiling point because the carbon number of alkyl is comparatively large.(methyl) alkyl acrylate that the carbon number of alkyl is little has lower boiling more, and the curable resin composition comprising so lower boiling (methyl) alkyl acrylate can not be used as the curable resin composition manufacturing Sparent laminate with the layered manner that reduces pressure.May be used for the curable resin composition of layered manner of reducing pressure, be better not containing boiling point under normal pressure be less than 150 DEG C, the preferably compound of less than 200 DEG C.
(additive (G))
As additive (G), UV light absorber (benzotriazole category, hydroxyphenyltriazinuv class etc.), photostabilizer (hindered amines etc.), pigment, dyestuff, metal oxide microparticle, filler etc. can be exemplified.
UV light absorber is the light deterioration in order to prevent curable resin composition, improves weathering resistance and uses, such as, can exemplify the UV light absorber etc. such as benzotriazole category, triazines, Benzophenones, benzoates.
As Benzotriazole Ultraviolet Stabilizer, such as can exemplify 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2,4-two (1-methyl isophthalic acid-phenylethyl)-6-(2H-benzotriazole-2-base) phenol, 2-(the chloro-2 benzotriazole of 5-)-6-Butylated Hydroxytoluene, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-) benzotriazole, (2,2-methylene-bis [6-(2H-benzotriazole-2-base)-4-(1,1,3,3,-tetramethyl butyl) phenol], 2-(2H-benzotriazole-2-base)-4, two (1,1-dimethyl propyl) phenol of 6-etc.
As triazine-based ultraviolet absorption agent, such as, can exemplify 2-[4,6-phenylbenzene-1,3,5-triazine-2-base]-5-(hexyloxy) phenol, 2-[4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines-2-base]-5-(different octyloxy) phenol etc.
As Benzophenones UV light absorber, such as, can exemplify 2-hydroxyl-4-n-octyloxy benzophenone, (2,4-dihydroxy phenyl) benzophenone etc.
As benzoates UV light absorber, such as, can exemplify 2-[4,6-phenylbenzene-1,3,5-triazines-2-base]-5-(hexyloxy) phenol etc.
Photostabilizer in order to prevent the deterioration of the light of curable resin composition, improve weathering resistance and use, such as, can exemplify the photostabilizer of hindered amines.
As the photostabilizer of hindered amines, such as, can exemplify following compound.
N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl)-N '-[4-[butyl (2, 2, 6, 6-tetramethyl--4-piperidyl) amino]-1, 3, 5-triazine-2-base]-1, 6-hexanediamine, succinic acid 1-[2-(4-hydroxyl-2, 2, 6, 6-tetramethyl piperidine subbase) ethyl] ester, 2-butyl-2-(4-hydroxyl-3, 5-di-t-butyl benzyl) propanedioic acid two (1, 2, 2, 6, 6-pentamethvl-4-base) ester, sebacic acid two (1, 2, 2, 6, 6-pentamethvl-4-base) ester, sebacic acid two (2, 2, 6, 6-tetramethyl--4-piperidyl) ester, butane-1, 2, 3, 4-tetracarboxylic acid four (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 1, 2, 3, 4-BTCA four (2, 2, 6, 6-tetramethyl piperidine-4-base) ester, methacrylic acid 1, 2, 2, 6, 6-pentamethyl--4-piperidyl ester, methacrylic acid (1, 2, 2, 6, 6-pentamethvl-4-base) ester, methacrylic acid 2, 2, 6, 6-tetramethyl--4-piperidyl ester, 7-oxa--3, two volution [5.1.11.2] heneicosane-20-pyruvic acid 2 of 20-diaza, 2, 4, 4-tetramethyl--21-oxo-ten two/tetradecyl ester, 2, 2, 4, 4-tetramethyl--7-oxa--3, two volution [5.1.11.2]-heneicosane-21-ketone of 20-diaza, Beta-alanine N-(2, 2, 4, 4-tetramethyl--4-piperidyl)-ten two/tetradecyl esters, 2, 5-pyrrolidine-diones 3-dodecyl-1-(2, 2, 6, 6-tetramethyl--4-piperidyl), 2, 5-pyrrolidine-diones N-ethanoyl-3-dodecyl-1-(2, 2, 6, 6-tetramethyl--4-piperidyl).
Antioxidant is the oxidation in order to prevent curable resin composition, improves weathering resistance, thermotolerance and the compound used, such as, can exemplify phenol, Phosphorus antioxidant etc.
As the antioxidant of phenol, such as, can exemplify following compound.
Tetramethylolmethane four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2, two [the 3-(3 of 2 '-thiodiethyl, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3-(3, 5-di-tert-butyl-hydroxy phenyl) the stearic alcohol ester of propionic acid, N, N '-(1, 6-dihexyl) two [3, 5-two (1, 1-dimethyl ethyl)-4-hydroxybenzene propionic acid amide], octyl group-3, 5-di-t-butyl-4-hydroxy-hydrocinnamic acid, 2, 4, 6-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) trimethylbenzene, two [3, 5-bis-(tertiary butyl)-4-hydroxybenzyl (oxyethyl group) phosphonous acid] calcium, 2, two (octylsulfo the methyl)-6-methylphenol of 4-, 2, two [(octylsulfo) the methyl]-6-methylphenol of 4-, two [3-(1, 1-dimethyl ethyl)-4-hydroxy-5-methyl base phenylpropionic acid] ethylenebis (oxygen base-2, 1-second two base) ester, 1, 6-hexylene glycol-bis-[3 (3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 1, 3, 5-tri-[[3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl]-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 1, two [the 4-(1 of 1 '-imino-, 1, 3, 3-tetramethyl butyl) benzene], 4-[[4, two (octylsulfo)-1 of 6-, 3, 5-triazine-2-base] amino]-2, 6-DI-tert-butylphenol compounds, diethyl { [3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl } phosphonic acid ester.
As phosphorus antioxidants, such as, can exemplify following compound.
Triphenyl phosphite, diphenylisodecyl base ester, diisodecyl phenyl phosphite, 4, 4 '-butylidene-bis-(3-methyl-6-tert butyl phenyl two (tridecyl)) phosphorous acid ester, two (nonyl phenyl) phosphorous acid ester of ring neopentane four base, two (dinonylphenyl) phosphorous acid ester of ring neopentane four base, ring neopentane four base three (nonyl phenyl) phosphorous acid ester, ring neopentane four base three (dinonylphenyl) phosphorous acid ester, 10-(2, 5-dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, diphosphorous acid diiso decyl pentaerythritol ester, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, phosphorous acid two (2, 4-di-t-butyl-6-aminomethyl phenyl)-ethyl ester, the two [(the 2-tertiary butyl-5-methyl-4 of butylidene, 1-phenylene) oxygen base] two (phosphonous acid two (tridecyl) ester).
In curable resin composition of the present invention described above, the oligopolymer (A), compound (B), sulfhydryl compound (D) and the Photoepolymerizationinitiater initiater that obtain owing to comprising the above-mentioned polyvalent alcohol (a1) of use, therefore, it is possible to the curable resin composition that the physical property obtaining the cured article that the storage time before because of solidification causes is with low uncertainty.
< Sparent laminate >
Sparent laminate of the present invention has a pair transparency carrier and is held on this to the curing resin layer between transparency carrier.Curing resin layer is the layer formed by the cured article of curable resin composition of the present invention.
As transparency carrier, sheet glass or resin board can be exemplified.If use sheet glass, then laminated glass can be obtained.If use polycarbonate plate as resin board, then can obtain the high and transparent panel of light weight of shock-resistance.In addition, also sheet glass and resin board can be combined and use.
The size of transparency carrier is not particularly limited, as long as have at least one more than 300mm, be better the transparency carrier on limit of more than 600mm, then can be widely used as for building or for motor vehicle transparent component being arranged at opening portion.In common purposes, 4m 2following size is more suitable.
The thickness preferably 0.2 ~ 4.0mm of curing resin layer.If the thickness of curing resin layer is more than 0.2mm, then the physical strength of Sparent laminate is good.
In Sparent laminate of the present invention described above, because the curing resin layer be clamped between transparency carrier is formed by the cured article of curable resin composition of the present invention, therefore the transparency is good, and resistance to tearing and the impact absorbency of the adaptation between transparency carrier and curing resin layer and curing resin layer are excellent.
The manufacture method > of < Sparent laminate
Sparent laminate of the present invention can by known manufacture method (such as, curable resin composition is clamped between a pair transparency carrier, make the method etc. that this curable resin composition solidifies) manufacture, be better by manufacturing by the manufacture method of decompression layered manner.Decompression layered manner is described in No. 08/081838th, International Publication and No. 09/016943rd, International Publication.
The feature of decompression layered manner is: the layer forming curable resin composition on one piece of transparency carrier, under reduced atmosphere on the layer of curable resin composition another block transparency carrier overlapping, curable resin composition is enclosed between two pieces of transparency carriers, then be placed in the atmosphere (being generally atmospheric pressure atmosphere) higher than the pressure of above-mentioned reduced atmosphere, curable resin composition is solidified.Therefore, the manufacture method of Sparent laminate of the present invention must adopt the first following operation and the second operation.
First operation: the layer forming curable resin composition on one piece of transparency carrier, under reduced atmosphere on the layer of curable resin composition another block transparency carrier overlapping, manufacture the operation of the duplexer precursor that there is a pair transparency carrier and be enclosed in the above-mentioned curable resin composition between this pair transparency carrier.
Second operation: above-mentioned duplexer precursor is placed in the atmosphere higher than the pressure of above-mentioned reduced atmosphere, and under this atmosphere, make the operation that described curable resin composition solidifies.
Reduced atmosphere in first operation is better the pressure atmosphere of below 1kPa, more preferably the pressure atmosphere of below 100Pa.In addition, if the hypotony of reduced atmosphere, then the composition that the boiling point in curable resin composition is lower likely volatilizees, therefore, and the pressure atmosphere of reduced atmosphere preferably more than 1Pa, the more preferably pressure atmosphere of more than 10Pa.
As the atmosphere that the pressure of the above-mentioned reduced atmosphere of ratio in the second operation is high, the preferably pressure atmosphere of more than 50kPa, the more preferably pressure atmosphere of more than 100kPa.Pressure atmosphere in second operation is generally atmospheric pressure atmosphere.Below, the situation being atmospheric pressure atmosphere for the atmosphere higher than the pressure of above-mentioned reduced atmosphere is described this manufacture method.
In first operation, even if having gas bubbles left in the curable resin composition in enclosed space, this bubble also evanescence before curable resin composition solidification, easily obtains bubble-free curing resin layer.That is, when being placed under normal atmosphere by the duplexer formed in the first operation precursor, also pressure is applied to the curable resin composition in enclosed space by the pressure from the transparency carrier under normal atmosphere.On the other hand, under being in the reduced atmosphere pressure of the first operation because the bubble in curable resin composition is inner, so by making the volume-diminished of this bubble to curable resin composition applied pressure in the second operation, in addition, because the gas dissolving in bubble is in curable resin composition, so bubble collapse.In order to make bubble collapse, be better duplexer precursor remained on for some time under normal atmosphere before making curable resin composition solidify.Preferably more than 5 minutes hold-time, when not having bubble or bubble very little and to rapidly disappear etc., the hold-time can also shorten further.
In the first operation, reduced atmosphere is required in the stage of formation enclosed space, and the stage is before this optional.Such as, the sealing material of specific thickness is set at the whole peripheral part of the one side of side transparency carrier, when supplying curable resin composition to form cured resin composition layer to the transparency carrier surface impaled by sealing material, these stages can carry out under atmospheric pressure atmosphere.The formation of enclosed space is better carried out according to following method.
Transparency carrier by the transparency carrier and opposite side with cured resin composition layer obtained above is put into underpressure chamber, and forms the configuration of regulation.Namely, the transparency carrier with cured resin composition layer is placed on upward on the platform of level cured resin composition layer, the transparency carrier of opposite side is arranged at the lower surface of the levelling bench installed on the top of inflator moving up and down (cylinder), and the state do not contacted with the transparency carrier of opposite side with cured resin composition layer makes two transparency carriers be positioned at parallel position.Then, close underpressure chamber and be exhausted, make inside, underpressure chamber reach the reduced atmosphere of regulation.After inside, underpressure chamber reaches the reduced atmosphere of regulation, make inflator work, two transparency carriers are situated between overlapping with cured resin composition layer, curable resin composition is enclosed within the space impaled by two transparency carriers and sealing material, thus form duplexer precursor.After forming duplexer precursor, make inside, underpressure chamber return to atmospheric pressure atmosphere, and duplexer precursor is taken out from underpressure chamber.
As long as the dhering strength between two transparency carriers and sealing material reaches the degree that gas when being placed under normal atmosphere by duplexer precursor can not enter from the interface of transparency carrier and sealing material.Such as, can sealant surface arrange pressure-sensitive adhesive layer with make transparency carrier and sealing material closely sealed.In addition, the caking agent of solidified nature can be set at the interface of transparency carrier and sealing material as required, or with the resin formation sealing material of solidified nature, after formation duplexer precursor, these caking agents or curable resin is made to solidify the dhering strength improved between transparency carrier and sealing material in inside, underpressure chamber or after underpressure chamber taking-up duplexer precursor.
Second operation is the operation under above-mentioned duplexer precursor is placed in normal atmosphere, curable resin composition being solidified.The curable resin composition of the invention described above is the composition of the light solidified comprising Photoepolymerizationinitiater initiater, so can make curable resin composition photocuring by irradiating light to above-mentioned duplexer precursor.Photocuring is by being undertaken irradiating implementing by the light transmission sent by light sources such as ultraviolet lamps transparency carrier.As mentioned above, be better, after duplexer precursor is remained on normal atmosphere lower for some time, curable resin composition is solidified.By making curable resin composition solidify, curable resin composition becomes cured resin, thus obtains Sparent laminate as above.
Below, based on Fig. 1, one example of the manufacture method of Sparent laminate of the present invention is described.
In first operation, edge section on the transparency carrier 10 (hereinafter referred to as " transparency carrier 10 ") of a side arranges sealing material 12 in the mode spreading all over whole periphery, sealing material 12 is coated with sealing uv curing resin 36, curable resin composition 14 is supplied on the surface of the transparency carrier 10 impaled by sealing material 12, make the layer of curable resin composition 14 upward, level is placed in underpressure chamber 26.In addition, in underpressure chamber 26, on the upper mounting plate 30 utilizing inflator 34 that the transparency carrier 16 (hereinafter referred to as " transparency carrier 16 ") of the opposing party is remained on by absorption layer 32 to move up and down, make it relative abreast above transparency carrier 10.Close underpressure chamber 26, start vacuum pump 28 and be exhausted, make the reduced atmosphere reaching regulation in underpressure chamber 26.Then, start inflator 34, transparency carrier 16 is fallen, is clamped the layer of curable resin composition 14 by transparency carrier 10 and transparency carrier 16, form curable resin composition 14 by transparency carrier 10 and transparency carrier 16 and the airtight duplexer precursor of sealing material 12.
In second operation, make to return to atmospheric pressure atmosphere in underpressure chamber 26, above-mentioned duplexer precursor is taken out from underpressure chamber 26, under atmospheric pressure atmosphere, by rayed, the curable resin composition of above-mentioned duplexer precursor is solidified, obtain Sparent laminate.
Embodiment
By the following examples the present invention is described in detail, but the present invention is not limited to these embodiments.
Hydroxyl value is the value calculated according to JIS K1557-1 (version in 2007).
[Production Example 1: the manufacture of polyoxyalkylene polyol]
Use the voltage-resistant reactor possessing stirrer and nitrogen ingress pipe, using zinc hexacyanocobaltate-glyme complex compound as catalyzer, under nitrogen atmosphere, at 130 DEG C while propylene oxide is slowly added in initiator propylene glycol while make it react, after making catalyst deactivation, adopt potassium hydroxide as catalyzer, then make reacting ethylene oxide.Resultant is extracted out from reaction vessel, obtains polyoxyalkylene polyol.Poly-(oxypropyleneoxyethylene) glycol that the polyoxyalkylene polyol obtained is average hydroxyl number is 2, hydroxyl value is 28.7mgKOH/g, oxyethylene group content is 24 quality %.
[embodiment 1]
Poly-(oxypropyleneoxyethylene) glycol, the 32.9g isophorone diisocyanate (be below denoted as IPDI) that by Production Example 1 are obtained of 460.3g as polyvalent alcohol is added in the reaction vessel possessing stirrer and nitrogen ingress pipe, further interpolation 0.039g distearyl acid dioctyl tin (being denoted as DOTDS below), make it in 70 DEG C of reactions 10 hours, obtain isocyanate group terminal carbamate ester prepolymer (INDEX=1.22).
Then, add in this isocyanate group terminal carbamate ester prepolymer 0.135g dibutyl tin dilaurate (being denoted as DBTDL below), 0.15g 2,5-di-tert-butyl hydroquinone (being denoted as DtBHQ below), 6.4g vinylformic acid 2-hydroxyl ethyl ester (being denoted as HEA below), by the NCO titration based on JIS K1603-1 while carry out the mensuration of isocyanate group containing ratio, while carry out reacting until isocyanate group disappears, obtain unsaturated urethane origoester acrylate.Below, the unsaturated urethane origoester acrylate obtained is called oligopolymer (A1).
Add oligopolymer (A1) that 40g obtains, 30g vinylformic acid 4-hydroxy butyl ester (being denoted as 4HBA below), 30g lauryl alcohol ester (being denoted as LA below), 3g as the 1-hydroxy cyclohexyl phenylketone (being denoted as HCHPK below) of light trigger, 0.3g as IRGANOX-1010 (BASF AG (BASF society) system), the 0.04g of antioxidant as DtBHQ, 0.8g of polymerization starter as the 1-decyl mercaptan of sulfhydryl compound (D), mix, obtained curable resin composition.
[embodiment 2 ~ 9, comparative example 1 ~ 3]
The sulfhydryl compound (D) of embodiment 1 and addition are changed into the use level recorded in table 2 ~ table 4, the curable resin composition of obtained embodiment 2 ~ 9, comparative example 1 ~ 3.
In addition, " チ オ カ Le コ mono-Le " in table is the trade(brand)name of 1-decyl mercaptan, and " カ レ Application ズ PE-1 " is the trade(brand)name of four (3-mercaptobutyric acid) pentaerythritol ester.
[table 1]
[table 2]
[table 3]
[table 4]
[evaluation]
(storage modulus)
For the curable resin composition obtained by embodiment 1 ~ 9 and comparative example 1 ~ 3, the rheometer MCR-301 made with Anton Paar Co., Ltd. (Antonpaar society), measures with HgXe (100mW/cm 2) lamp solidifies the storage modulus after 1 minute (G ').Condition determination adopts sample thickness 0.4mm, frequency 1Hz, deformation 1%, temperature 35 DEG C.
(storage stability)
The Photocurable resin composition of embodiment 1 ~ 9 and comparative example 1 ~ 3 is got the brown phial that about 80ml puts into 100ml respectively, keeping 1 day and after 2 days in the stove of 85 DEG C, mensuration storage modulus (G '), analyze the elastic modulus change that the storage modulus before keeping occurs.
Velocity of variation (%)=[G ' at (G ' at the G '-initial stage in 85 DEG C of stoves after keeping)/initial stage] × 100 of storage modulus (G ')
The velocity of variation of storage modulus after 2 days (G ') is less than 30% be denoted as ◎, is denoted as zero, is denoted as △ more than 50% to 80% more than 30% below 50%, be denoted as more than 80% ×.
(smell)
Allow 2 appraisers smell the smell of the Photocurable resin composition hearing embodiment 1 ~ 9 and comparative example 1 ~ 3, feel scentless and be denoted as zero, what have unhappy smell a little is denoted as △, and what unhappy smell was strong be denoted as ×.
[result]
Described in table 2 ~ table 4, the curable resin composition that with the addition of the sulfhydryl compound (D) that embodiment is recorded, compared with comparative example, obtains the curable resin composition of storage stability, excellent smell.The storage stability not adding the comparative example 1 of sulfhydryl compound (D) is poor.Molecular weight corresponding to each-SH base is at the extraneous comparative example 2 of the present application and carbon number corresponding to each-SH base at the extraneous comparative example 3 of the present application, and the storage modulus G ' at its initial stage is although can reduce, and storage stability is poor.
The possibility that industry utilizes
Curable resin composition of the present invention can be used as the raw material of the adhesive resin layer of laminated glass, and Sparent laminate of the present invention can be used for laminated glass (windshield glass, shatter proof glass, burglar-proof glazing etc.), display applications, solar cell purposes etc.
Here the announcement of full content as specification sheets of the present invention of the specification sheets of No. 2012-162536, the Japanese patent application that on July 23rd, 2012 files an application, claims, summary and accompanying drawing is quoted.
Nomenclature
10,16 ... transparency carrier, 12 ... sealing material, 14 ... curable resin composition, 26 ... underpressure chamber, 28 ... vacuum pump, 30 ... upper mounting plate, 32 ... absorption layer, 34 ... inflator, 36 ... sealing uv curing resin.

Claims (14)

1. curable resin composition, it comprises following unsaturated urethane oligopolymer (A), has the compound (B) of 1 following solidified nature functional group and 1 hydroxyl, following sulfhydryl compound (D) and Photoepolymerizationinitiater initiater;
Solidified nature functional group: with CH 2the group that=C (R) C (O) O-represents, wherein R represents hydrogen atom or methyl;
Unsaturated urethane oligopolymer (A): the compound (a3) making polyoxyalkylene polyol (a1), polyisocyanates (a2) and have described solidified nature functional group and a hydroxyl carries out reacting and the unsaturated urethane oligopolymer obtained under the existence of organo-tin compound, or the compound (a4) making polyoxyalkylene polyol (a1) and have described solidified nature functional group and an isocyanate group carries out reacting and the unsaturated urethane oligopolymer obtained under the existence of organo-tin compound;
Sulfhydryl compound (D): the molecular weight that every 1-SH base is corresponding is uncle's sulfhydryl compound (D1) of 70 ~ 420, or molecular weight corresponding to every 1-SH base is the secondary sulfhydryl compound (D2) of 28 ~ 420.
2. curable resin composition as claimed in claim 1, it is characterized in that, described solidified nature functional group is acryloxy.
3. curable resin composition as claimed in claim 1 or 2, it is characterized in that, every 1 molecule of described unsaturated urethane oligopolymer (A) on average has 2 ~ 3 described solidified nature functional groups.
4. the curable resin composition according to any one of claims 1 to 3, it is characterized in that, described polyoxyalkylene polyol (a1) is average hydroxyl number is 2 ~ 3, hydroxyl value is 15 ~ 30mgKOH/g, oxyethylene group content is 8 ~ 50 quality % poly-(oxypropyleneoxyethylene) polyvalent alcohol.
5. the curable resin composition according to any one of Claims 1 to 4, is characterized in that, described polyisocyanates (a2) is alicyclic ring same clan vulcabond or aliphatic category vulcabond.
6. the curable resin composition according to any one of Claims 1 to 5, is characterized in that, described compound (a3) is the hydroxyalkyl acrylate of the hydroxyalkyl with carbon number 2 ~ 12.
7. the curable resin composition according to any one of claim 1 ~ 6, is characterized in that, described organo-tin compound is organotin carboxylate.
8. the curable resin composition according to any one of claim 1 ~ 7, is characterized in that, described compound (B) has the vinylformic acid list hydroxyalkyl that carbon number is the hydroxyalkyl of 3 ~ 8.
9. the curable resin composition according to any one of claim 1 ~ 8, is characterized in that, described sulfhydryl compound (D1) is aliphatics sulfhydryl compound.
10. the curable resin composition according to any one of claim 1 ~ 8, is characterized in that, described sulfhydryl compound (D2) is the aliphatics sulfhydryl compound of carbon number 3 ~ 40 or the alicyclic sulfhydryl compound of carbon number 3 ~ 40.
11. curable resin compositions according to any one of claim 1 ~ 10, is characterized in that, also comprise and have the compound (C) that 1 described solidified nature functional group and carbon number are the alkyl of 8 ~ 22.
12. curable resin compositions according to any one of claim 1 ~ 11, it is characterized in that, described curable resin composition contains the sulfhydryl compound (D) of the unsaturated urethane oligopolymer (A) of 20 ~ 75 quality %, the compound (B) of 10 ~ 50 quality % and 0.05 ~ 3.0 quality %.
13. Sparent laminates, it is the Sparent laminate of the layer having a pair transparency carrier and be clipped in the cured resin between this transparency carrier, it is characterized in that, described cured resin is the cured article of the curable resin composition according to any one of claim 1 ~ 12.
The manufacture method of 14. Sparent laminates, it is characterized in that, there is following first operation and the second operation, first operation: the layer forming the curable resin composition according to any one of claim 1 ~ 12 on one piece of transparency carrier, under reduced atmosphere on the layer of described curable resin composition another block transparency carrier overlapping, manufacture the duplexer precursor that there is a pair transparency carrier and be enclosed in the described curable resin composition between this pair transparency carrier; Second operation: described duplexer precursor is placed in the atmosphere higher than the pressure of described reduced atmosphere, makes described curable resin composition solidify under this atmosphere.
CN201380039063.1A 2012-07-23 2013-07-12 Curable resin composition, transparent laminate and method for producing transparent laminate Pending CN104487470A (en)

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