CN104755579A - Photocurable material for sealing, sealing method, sealing material, and case using sealing material - Google Patents

Photocurable material for sealing, sealing method, sealing material, and case using sealing material Download PDF

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Publication number
CN104755579A
CN104755579A CN201380056600.3A CN201380056600A CN104755579A CN 104755579 A CN104755579 A CN 104755579A CN 201380056600 A CN201380056600 A CN 201380056600A CN 104755579 A CN104755579 A CN 104755579A
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China
Prior art keywords
methyl
sealing material
acrylate
light solidified
solidified sealing
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Granted
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CN201380056600.3A
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Chinese (zh)
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CN104755579B (en
Inventor
中谷裕之
上野精记
关田和昌
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Bostik SA
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Nitta Gelatin Inc
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Priority claimed from PCT/JP2012/078297 external-priority patent/WO2013080737A1/en
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1062—UV-curable materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Sealing Material Composition (AREA)

Abstract

This photocurable material for sealing, which contains (A) an oligomer that contains a (meth)acryloyl group and has a weight average molecular weight of 10,000-30,000, (B) a (meth)acrylate monomer, (C) a polythiol compound, and if necessary, (D) a carbodiimide compound, has high recoverability from compression, high tensile strength, excellent flexibility, and if necessary, low hardness. Consequently, this photocurable material for sealing is capable of providing a sealing material that exhibits excellent sealing characteristics such as excellent airtightness and waterproof properties, while having less surface tackiness, and the like.

Description

Its housing of light solidified sealing material, sealing method, sealing material and use
Technical field
The present invention relates to its housing of light solidified sealing material, sealing method, sealing material and use.The present invention, more particularly, relates to and utilizes ultraviolet etc. simple and easy and the light solidified sealing material being cured to deep instantaneously.
Background technology
In the housing of the precision equipments such as family's electrical article, photographic camera, clock and watch such as the electronic productses such as mobile telephone, digital camera, pick up camera, refrigerator, air-conditioning, washing machine etc., in recent years client for have water-repellancy, the contour sealing characteristics of resistance to air loss the requirement of goods surging.In addition, such as, for mobile telephone, employed the resin that nylon/GF etc. is hard in the past, in recent years, employed the resins for universal use such as ABS or ABS/PC of cheaper.But, due to softnesses such as ABS or ABS/PC, be easily out of shape, therefore for sealing material in the past, there is the problem that cannot obtain sufficient sealing characteristics.Therefore, the sealing material that flexibility and tensile strength are high compared with sealing material is in the past required.
As sealing material in the past, known such as hotmelt, 1 liquid type carbamate system reaction type hot melt adhesives, Thermoplastic hot melt's sealing material, moisture-curable hot-melting sealed material, Thermocurable sealing material, molded rubber sealing material (packing ring) and 2 liquid type carbamate systems foaming sealing material etc.But, the operability of equal difference that what all also the thermotolerance water-repellancy etc. of Shortcomings, moisture were mixed into prevent, device for heating, the damage of heat of housing, the problem such as operability of difference that uses the manufacture of mould to produce, when using the resins for universal use of particularly soft in the housing of electronic products, family's electrical article, precision equipment etc., the performance that can allow to fully satisfy the demand is not had to manifest.
Light solidified sealing material is made sealing material owing to not using mould on housing, and therefore compared with sealing material in the past, operability is excellent.In light solidified sealing material, main exist the photocuring sealing material of the radical polymerization adopting acryl and adopt the alkene-mercaptan system photocuring sealing material of alkene-thiol reactant.Adopt the light solidified sealing material of the radical polymerization of acryl; such as; be recorded in patent documentation 1 and 2, to use up etc. make to comprise urethane acrylate oligomer, acrylate monomer, Photoepolymerizationinitiater initiater (and light sensitizer) composition solidification and generate.But the light solidified sealing material of patent documentation 1 and 2 does not have the enough flexibilities required by housing and the tensile strength of electronic products, family's electrical article, precision equipment etc.
Alkene-mercaptan system photocuring sealing material, such as, is recorded in patent documentation 3 ~ 6.In patent documentation 3, disclose containing polyenoid, polythiol and the Photocurable resin composition of compound with the aromatic nucleus that bromine replaces, the cured article describing this composition has high refractive index, and bonding strength, surface cure are excellent, can adjust with high precision refractive index.Patent Document 4 discloses containing polyenic compounds and the alkene-mercaptan system photocurable resin composition of (many) mercaptan system monomer comprising poly-mercaptan carboxylic acid's amide compound, describe this composition and there is not the inhibition that oxygen causes, can solidify with the short period of time, volumetric shrinkage is little, can reduce the usage quantity of light trigger, and wet fastness improves significantly.Patent Document 5 discloses the solidification compound of the mercaptan compound of the group comprised containing more than 2 ad hoc structures and the carbamate compounds containing ethylenic unsaturated double-bond of ad hoc structure, describe the adaptation of the cured article of this composition and base material, reactivity and the transparency high, thermotolerance and hardness are also high.Patent Document 6 discloses containing polyhutadiene (methyl) acrylate, multi-thioalcohol compound and optical free radical initiator, the Photocurable resin composition solidified by the irradiation of ultraviolet LED, describe the quick solidifying of this composition, surface cure is excellent, and wet fastness, resistance to air loss are excellent.But, patent documentation 3 ~ 6 for electronic products, family's electrical article, precision equipment etc. housing required by flexibility, tensile strength etc., all without any mentioning.
For the light solidified sealing material of carry out acryl Raolical polymerizable and alkene-thiol reactant with competing simultaneously, be recorded in patent documentation 7 and 8.In patent documentation 7 and 8; disclose and comprise (A) and have the oligopolymer of (methyl) acryl, (B) (methyl) acrylate monomer and (C) multi-thioalcohol compound, the functional group number of acryl and sulfydryl is than for 100:0.1 ~ 100:5n, (n is the number of the sulfydryl in multi-thioalcohol compound 1 molecule.) packing ring material.Describe this packing ring material and can improve elongation at break, the generation of be full of cracks, crackle etc. can be suppressed.In the embodiment of patent documentation 7, the concrete multi-thioalcohol compound used is all the compound with uncle's mercaptan, but the packing ring material cured thing obtained in embodiment is all any portion deficiency of flexibility, elongation at break (tensile strength), compression recovery rate, in embodiment, fail to find whole function meeting the degree that can use in the housing of electronic products, family's electrical article, precision equipment etc.In addition, chase after the sealing material recorded in the table 2 of examination patent documentation 7, result has stopped to manufacture as the energy-line solidifying type oligopolymer A (chemistry society of common prosperity society system, trade(brand)name " ラ イ ト タ ッ Network PUA-KH32M ") of raw material.Therefore, contained oligopolymer and monomer suitably mixed and chase after examination, result, as recorded in the comparative example of this specification sheets, only obtains the extremely hard sealing material that hardness is more than 50, is not suitable for as the sealing material for housing.
Prior art document
Patent documentation
No. 1:WO96/10594, patent documentation
Patent documentation 2: JP 2004-26919 publication
Patent documentation 3: JP 2003-277505 publication
Patent documentation 4: JP 2007-70417 publication
No. 5:WO2007/086461, patent documentation
No. 6:WO2010/071171, patent documentation
Patent documentation 7: JP 2010-260918 publication
No. 8:WO2010/126040, patent documentation
Summary of the invention
The problem that invention will solve
The problem that the present invention will solve is to provide has high compression recovery rate, high tensile strength, excellent elongation, and have low hardness as required, the sealing characteristics such as resistance to air loss, water-repellancy is excellent thus, and the sealing material that surface viscosity is little.In addition, be also to provide simple and easy and be cured to the deep of light solidified sealing material instantaneously and generate sealing material, have until the light solidified sealing material of the good storage stability used.
For solving the means of problem
The present inventor is in order to solve above-mentioned problem; further investigation; found that; if make to comprise (A) weight-average molecular weight for 10 with specific ratio; 000 ~ 30; the oligopolymer with (methyl) acryl, (B) (methyl) acrylate monomer of 000 carry out photocuring with the light solidified sealing material of (C) multi-thioalcohol compound; unexpectedly compared with the sealing material recorded in any patent documentation; tensile strength (elongation at break) is very high; also there is high compression recovery rate simultaneously, complete the present invention.That is, the present invention is as described below.
[1] light solidified sealing material, that to comprise (A) weight-average molecular weight be 10, 000 ~ 30, the oligopolymer with (methyl) acryl of 000, (B) the light solidified sealing material of (methyl) acrylate monomer and (C) multi-thioalcohol compound, wherein there is relative to (A) oligopolymer 100 weight part of (methyl) acryl, comprise (B) (methyl) acrylate of 5 ~ 100 weight parts, (A) having (methyl) acryl contained in the oligopolymer of (methyl) acryl and (B) (methyl) both acrylate monomers with the ratio of the number existed in light solidified sealing material of the sulfydryl of (C) multi-thioalcohol compound is that (n is the number of the sulfydryl in multi-thioalcohol compound 1 molecule to 100:5n ~ 100:25n.)。
[2] the light solidified sealing material described in [1], wherein, has oligopolymer 100 weight part of (methyl) acryl, also comprises (D) carbodiimide compound of 0.1 ~ 15 weight part relative to (A).
[3] [1] or the light solidified sealing material described in [2], wherein, (C) multi-thioalcohol compound has 2 ~ 6 sulfydryls in 1 molecule, and its sulfydryl is secondary sulfydryl.
[4] [1] or the light solidified sealing material described in [2], wherein, (C) multi-thioalcohol compound is the ester generated by the polyvalent alcohol and β-mercaptobutyric acid with 2 ~ 6 hydroxyls.
[5] the light solidified sealing material described in any one of [1] ~ [4], wherein, (B) (methyl) acrylate monomer is simple function (methyl) acrylate, multifunctional (methyl) acrylate or their combination.
[6] the light solidified sealing material described in any one of [1] ~ [5]; wherein, (A) has the oligopolymer of (methyl) acryl is at least a kind that selects from the group comprising carbamate system (methyl) origoester acrylate, Polyester (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy (methyl) origoester acrylate, conjugated diolefin polymer system (methyl) origoester acrylate and their hydride.
[7] the light solidified sealing material described in any one of [1] ~ [6], wherein, also comprises (E) optical free radical polymerization starter and/or (F) viscosity adjusting agent.
[8] sealing method, it is undertaken by making the light solidified sealing material described in any one of [1] ~ [7] carry out photocuring.
[9] sealing material, it generates by making the light solidified sealing material described in any one of [1] ~ [7] carry out photocuring.
[10] housing, it uses the sealing material generated by making the light solidified sealing material described in any one of [1] ~ [7] carry out photocuring.
[11] for the stabilization agent of alkene-mercaptan system light-cured resin material, it contains carbodiimide compound.
The effect of invention
Utilize light solidified sealing material of the present invention, can provide the flexibility with high compression recovery rate, high tensile strength and excellence, the sealing characteristics such as resistance to air loss, water-repellancy is excellent thus, and the sealing material that surface viscosity is little.In addition, light solidified sealing material of the present invention can be cured to the deep of light solidified sealing material simple and easy and instantaneously and generate sealing material, and has until the good storage stability that uses.
Embodiment
Successively light solidified sealing material of the present invention is described.
(A) weight-average molecular weight is 10,000 ~ 30,000 there is (methyl) acryl oligopolymer
(A) weight-average molecular weight of oligopolymer is 10,000 ~ 30,000, and preferably, can enumerate weight-average molecular weight is 12,000 ~ 25, the oligopolymer of 000, and more preferably, can enumerate weight-average molecular weight is 15,000 ~ 22, the oligopolymer of 000.(A) oligopolymer, preferably, can be set forth in molecule and there is at least 2 (methyl) acrylate-based oligopolymer, (A) (methyl) in 1 molecule of oligopolymer acrylate-based number is such as 2 ~ 10, be preferably 2 ~ 6, be more preferably 2 ~ 4, be particularly preferably 2.
As the oligopolymer of (A), such as carbamate system (methyl) origoester acrylate, Polyester (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, acrylic acid series (methyl) origoester acrylate, epoxy (methyl) origoester acrylate, polybutadiene oligomer equiconjugate diene polymerization system (methyl) origoester acrylate and hydride etc. thereof, organosilicon (methyl) acrylate can be enumerated.
As carbamate system (methyl) origoester acrylate, polyvalent alcohols such as such as making polyether glycol, polyester polyol, carbonate diol can be enumerated and polyisocyanates reacts and obtains urethane oligomer, this oligopolymer be carried out esterification with (methyl) vinylformic acid and the oligopolymer that obtains.
As Polyester (methyl) origoester acrylate, can enumerate such as by making polycarboxylic acid and polyol condensating or by making the addition of polycarboxylic acid oxyalkylene, obtain the polyester oligomer at two ends with hydroxyl, its hydroxyl is carried out esterification and the oligopolymer that obtains with (methyl) vinylformic acid.
As polyethers system (methyl) origoester acrylate, the oligopolymer such as obtained by making the hydroxyl of polyether glycol (methyl) vinylformic acid carry out esterification can be enumerated.
As acrylic acid series (methyl) origoester acrylate, the distant pawl polyacrylic ester etc. of the control texture to heavens by the application of atom transfer radical polymerization (ATRP) method can be enumerated.
As epoxy (methyl) origoester acrylate, can enumerate such as by making that the oxyethane ring of (methyl) vinylformic acid and the lower bisphenol-type epoxy resin of molecular weight ratio and phenolic resin varnish type epoxy resin reacts, esterification and the oligopolymer obtained, also comprise the epoxy acrylate oligomer of the carboxy-modified type this epoxy (methyl) origoester acrylate partly being used dicarboxylic anhydride modification.
As conjugated diolefin polymer system (methyl) origoester acrylate, can enumerate such as aqueous styrene-butadiene copolymer vinylformic acid is carried out esterification and obtain SBR diacrylate, polyisoprene vinylformic acid is carried out esterification and obtain polyisoprene diacrylate, polyhutadiene vinylformic acid is carried out esterification and obtain PBAA ester, make to have in molecular end hydroxyl 1,2-polyhutadiene with there is (methyl) acrylate reactions of isocyanate group and the PBAA ester etc. that obtains.
As organosilicon (methyl) acrylate, the hydroxyl and acrylic acid ester cpds etc. of alcoholic silicone compounds can be enumerated.
(A) oligopolymer can be used alone a kind, also two or more can be combinationally used.As the oligopolymer of preferred (A), carbamate system (methyl) origoester acrylate can be enumerated, such as carbamate system polyester (methyl) origoester acrylate can be enumerated.
As preferred (A) oligopolymer, in carbamate system (methyl) origoester acrylate with 2 (methyl) acryls; the polyether glycol with 2 hydroxyls, polyester glycol and the carbonate diol that use in manufacturing as it, can enumerate following material.
As polyether glycol, such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and 1 can be enumerated, 3-butyleneglycol, 1, the polyether glycol etc. of 4-butyleneglycol, neopentyl glycol, cyclohexanedimethanol, the upper addition such as oxyethane or propylene oxide such as 2,2-two (4-hydroxy-cyclohexyl) propane, dihydroxyphenyl propane etc.
As polyester glycol, such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1 can be enumerated, 3-butyleneglycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, 1, the dicarboxylic acid such as 4-cyclohexanedimethanol, the upper compound of the addition such as oxyethane or propylene oxide such as 2,2-two (4-hydroxy-cyclohexyl) propane, dihydroxyphenyl propanes etc., the alcohol of 6-caprolactone addition and hexanodioic acid, sebacic acid, nonane diacid, dodecanedicarboxylic acids or anhydride reaction and the polyester glycol etc. that obtains.
As carbonate diol; can enumerate such as by diaryl carbonate class or dialkyl carbonates and 1 such as diphenyl carbonate, carbonic acid two (chloro-phenyl-) ester, carbonic acid dinaphthyl ester, phenyl-toluyl-carbonic ether, phenyl-chloro-phenyl--carbonic ether, 2-tolyl-4-tolyl-carbonic ether, methylcarbonate, diethyl carbonates; 6-hexylene glycol, neopentyl glycol, 1; 4-butyleneglycol, 1; the carbonate diol etc. be obtained by reacting of the glycolss such as 8-ethohexadiol, 1,4 cyclohexane dimethanol, 2-methyl propanediol, dipropylene glycol, a contracting dibutylene glycol.
(B) (methyl) acrylate monomer
As (methyl) acrylate monomer; (methyl) acrylate monomer with at least 1 (methyl) acryl can be set forth in molecule; particularly, the monofunctional monomer with 1 (methyl) acryl, two functional monomers with 2 (methyl) acryls can be enumerated, there is the trifunctional monomer of 3 (methyl) acryls, there are four functional monomers etc. of 4 (methyl) acryls.
As monofunctional monomer, such as methyl methacrylate can be enumerated, butyl methacrylate, vinylformic acid 2-phenoxy ethyl, ethoxylation 2-phenoxyethyl acrylate, vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, cyclic trimethylolpropane, vinylformic acid formal, P-carboxy ethyl acrylates, lauryl methacrylate(LMA), Isooctyl acrylate monomer, stearyl methacrylate, isodecyl acrylate, isobornyl methacrylate, benzyl acrylate, hydroxyl valeryl hydroxy new pentane acid ester diacrylate, ethoxylation 1,6 hexanediol diacrylate, dipropylene, Tricyclodecane Dimethanol diacrylate, ethoxylation dipropylene, neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, Ethoxylated bisphenol-A dimethacrylate, 2-methyl isophthalic acid, ammediol diacrylate, ethoxylation 2-methyl isophthalic acid, ammediol diacrylate, 2-butyl-2-ethyl-1,3-PD diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate phosphoric acid ester, three (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, ethoxylation tetramethylol methane tetraacrylate, two-trimethylolpropane tetra-acrylate, propoxylated pentaerithytol tetraacrylate, tetramethylol methane tetraacrylate, dipentaerythritol six acrylate, methacrylic ester, Hydroxyethyl Acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), tripropylene glycol dimethacrylate, BDO dimethacrylate, HDDMA, allylation cyclohexyldimethyl acrylate, isocyanuric acid ester dimethacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated glycerol trimethacrylate, trimethylolpropane trimethacrylate, three (acryloyl-oxyethyl) isocyanuric acid ester, with these combination of more than two kinds.
As two functional monomers, such as 1,6 hexanediol diacrylate, bisphenol A ethoxy acrylate, polyethyleneglycol diacrylate (200-600), tri (propylene glycol) diacrylate, neopentyl glycol propoxylated glycerine (2), ethoxylation (2) neopentylglycol diacrylate, dipropylene, TriMethylolPropane(TMP) ethoxylation (3) methyl ether diacrylate and these combination of more than two kinds can be enumerated.
As trifunctional monomer, such as Viscoat 295, TriMethylolPropane(TMP) propoxylation (5-20) triacrylate, propoxylation (4) glycerol tri-acrylate, ethoxylation (3) Viscoat 295, pentaerythritol propoxylate triacrylate and these combination of more than two kinds can be enumerated.
As four functional monomers, such as contracting two (TriMethylolPropane(TMP)) tetraacrylate, dipentaerythritol monohydroxypentaacrylate and these combination of more than two kinds can be enumerated.
(methyl) acrylate monomer can be used alone a kind, also two or more can be combinationally used.As preferred (methyl) acrylate monomer, monofunctional monomer can be enumerated, also the combination of preferred monofunctional monomer and two functional monomers.As preferred monomer, monofunctional monomer can be enumerated.
As the usage quantity of (methyl) acrylate, there is relative to (A) oligopolymer 100 weight part of (methyl) acryl, use the scope of 5 ~ 100 weight parts.By using the amount of this scope, the reduction of the viscosity of sealing agent of the present invention, flexibility, compression recovery rate, tensile strength can be improved.As the usage quantity of preferred (methyl) acrylate, the scope of 10 ~ 80 weight parts can be enumerated, more preferably, the scope of 40 ~ 70 weight parts can be enumerated.According to the purposes of sealing material of the present invention, in order to obtain the characteristics such as its viscosity, flexibility, compression recovery rate, tensile strength, kind and the usage quantity of (methyl) acrylate monomer can be adjusted aptly.
(C) multi-thioalcohol compound
As multi-thioalcohol compound, the compound such as in molecule with 2 ~ 10 sulfydryls can be enumerated, preferably, the compound with 2 ~ 6 sulfydryls can be set forth in molecule, more preferably, the compound with 3 ~ 4 sulfydryls can be set forth in molecule.
As multi-thioalcohol compound, the multi-thioalcohol compound recorded in such as patent documentation 3 ~ 8 can be enumerated.Below these multi-thioalcohol compounds are specifically described.
As multi-thioalcohol compound, can enumerate such as
A () comprises the multi-thioalcohol compound (C of hydrocarbon structure 2-20the aromatic-aliphatic polythiol classes such as aliphatics polythiol class, phenylenedimethylidyne two mercaptan such as alkane polythiol, the polythiol class that the halogen atom sulfydryl of the halohydrin affixture of alcohols is replaced, the multi-thioalcohol compound etc. comprising the hydrogen sulfide resultant of reaction of polyepoxide compound),
(b) contained (1)
(in formula, R 1and R 2represent hydrogen atom or C independently 1-10alkyl.M be 0,1 or 2, n be 0 or 1.) shown in ether structure multi-thioalcohol compound and
(c) contained (2)
(in formula, R 1, R 2, m with n be identical with above-mentioned implication.) shown in the multi-thioalcohol compound of ester structure.As compound preferred in these multi-thioalcohol compounds, (b) can be enumerated and comprise the multi-thioalcohol compound that the multi-thioalcohol compound of ether structure and (c) comprise ester structure, more preferably, the multi-thioalcohol compound that (c) comprises ester structure can be enumerated.
Comprise the multi-thioalcohol compound of hydrocarbon structure as (a), can enumerate 2,5-ethanthiol, 2,9-the last of the ten Heavenly stems two mercaptan, Isosorbide-5-Nitrae-bis-(1-mercaptoethyl) benzene etc.
Comprise the multi-thioalcohol compound of ether structure as (b), can enumerate and such as there is 2-mercaptoethyl ether, 2-mercaptopropyi ether, 3-mercaptopropyi ether, 2-mercaptobutyl ether, 3-mercaptobutyl ether, 4-mercaptobutyl ether, 5-sulfydryl amyl group ether, the isostructural compound of 5-sulfydryl hexyl ether.
Comprising the multi-thioalcohol compound of ester structure as (c), comprising by making the compound carrying out esterification as hydrogen atom at the carboxylic acid containing sulfydryl and the polyalcohols of the compound of the left-end point bonding of the structure of formula (2) and generate.
As the concrete example of hydrogen atom at the carboxylic acid containing sulfydryl of the compound of the left-end point bonding of the structure of formula (2), Thiovanic acid, 2 mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid, 3-thiohydracrylic acid, 3-sulfydryl-3-phenylpropionic acid, 3-sulfydryl-3 Methylbutanoic acid etc. can be enumerated, preferably, 3-mercaptobutyric acid, 3-sulfydryl-3-phenylpropionic acid, 3-sulfydryl-3 Methylbutanoic acid etc. can be enumerated, more preferably, 3-mercaptobutyric acid can be enumerated.
As the concrete example of polyvalent alcohol, C can be enumerated 2-20aklylene glycol (preferred C 2-10alkylidene group, its carbochain can branch.As an example, ethylene glycol, 1,3-PD, 1 can be enumerated, 2-propylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, 1,12-dodecanediol, hexanaphthene-Isosorbide-5-Nitrae-dimethanol, Hydrogenated Bisphenol A etc.), glycol ether, poly-(oxyalkylene) glycol, glycerine, triglycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene ether diol, TriMethylolPropane(TMP), one contracting two (TriMethylolPropane(TMP)s), tetramethylolmethane, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, norbornylene dimethanol, norbornane dimethanol, polycarbonate diol, two terminal hydroxyl poly organic silicons, polyvalent alcohol containing aromatic nucleus, three-2-hydroxyethyl isocyanuric acid esters, 2, two [4-(2-hydroxyl-oxethyl) phenyl] propane of 2-, Hydrogenated Bisphenol A, 4, 4 '-(9-fluorenes fork base) two (2-phenoxyethyl alcohol), hexanaphthene-1, 4-dimethanol ethylene oxide adduct, hydrogenated bisphenol A epoxy ethane additive product, hexanaphthene-1, 4-dimethanol propylene oxide adduct, hydrogenated bisphenol A epoxy propane affixture etc.
As preferred polyvalent alcohol, ethylene glycol, 1 can be enumerated, 2-propylene glycol, 1, the carbon number of the alkylen backbone such as 2-butyleneglycol is aklylene glycol, TriMethylolPropane(TMP), polycarbonate diol, cyclohexanediol, the cyclohexanedimethanol, 1 of 2,5-pentanediol etc., as the polyvalent alcohol containing aromatic nucleus, can 2 be enumerated, two [4-(2-hydroxyl-oxethyl) phenyl] propane, 4 of 2-, 4 '-(9-fluorenes fork base) biphenol, 4,4 '-(9-fluorenes fork base) two (2-phenoxyethyl alcohols) etc.
As the example of these multi-thioalcohol compounds, can enumerative (3) and formula (4)
(in formula, R 3~ R 6represent hydrogen atom or C independently 1-10alkyl.L-C (O)-O-represents the structure shown in above-mentioned formula (2).) shown in multi-thioalcohol compound.As the R in formula (3) 3~ R 6c 1-10alkyl, the C of preferred straight chain or branched chain 1-3alkyl, particularly, can enumerate methyl, ethyl, n-propyl, sec.-propyl etc., wherein preferable methyl, ethyl.Particularly preferably R 3for hydrogen atom, methyl or ethyl, R 4~ R 6it is all the multi-thioalcohol compound of hydrogen atom.
As the concrete example of these multi-thioalcohol compounds, phthalic acid two (1-mercapto ethyl ester) can be enumerated, phthalic acid two (2-sulfydryl propyl ester), phthalic acid two (3-sulfydryl butyl ester), phthalic acid two (3-mercaptoisobutanoic ester), ethylene glycol bis (3-mercaptobutylate), propylene glycol two (3-mercaptobutylate), glycol ether two (3-mercaptobutylate), butyleneglycol two (3-mercaptobutylate), ethohexadiol two (3-mercaptobutylate), trimethylolpropane tris (3-mercaptobutylate), tetramethylolmethane four (3-mercaptobutylate), dipentaerythritol six (3-mercaptobutylate), 1,3 butylene glycol two (3-mercaptobutylate), BDO two (3-mercaptobutylate), neopentyl glycol two (3-mercaptobutylate), 1,6-hexylene glycol two (3-mercaptobutylate), 1,8-ethohexadiol two (3-mercaptobutylate), 1,9-nonanediol two (3-mercaptobutylate), hexanaphthene-Isosorbide-5-Nitrae-dimethanol two (3-mercaptobutylate), glycol ether two (3-mercaptobutylate), triglycol two (3-mercaptobutylate), polyoxyethylene glycol two (3-mercaptobutylate), dipropylene glycol two (3-mercaptobutylate), tripropylene glycol two (3-mercaptobutylate), polypropylene glycol two (3-mercaptobutylate), polytetramethylene ether diol two (3-mercaptobutylate), two (the 3-mercaptobutylate) of hexanaphthene-Isosorbide-5-Nitrae-dimethanol ethylene oxide adduct, two (the 3-mercaptobutylate) of hydrogenated bisphenol A epoxy ethane additive product, two (the 3-mercaptobutylate) of hexanaphthene-Isosorbide-5-Nitrae-dimethanol propylene oxide adduct, two (the 3-mercaptobutylate) of hydrogenated bisphenol A epoxy propane affixture, glycerine three (3-mercaptobutylate), two glycerine four (3-mercaptobutylate), trimethylolpropane tris (3-mercaptobutylate), one contracting two (TriMethylolPropane(TMP)) four (3-mercaptobutylate), tetramethylolmethane four (3-mercaptobutylate), dipentaerythritol six (3-mercaptobutylate), ethylene glycol bis (2 mercaptopropionic acid ester), propylene glycol two (2 mercaptopropionic acid ester), glycol ether two (2 mercaptopropionic acid ester), butyleneglycol two (2 mercaptopropionic acid ester), ethohexadiol two (2 mercaptopropionic acid ester), trimethylolpropane tris (2 mercaptopropionic acid ester), tetramethylolmethane four (2 mercaptopropionic acid ester), dipentaerythritol six (2 mercaptopropionic acid ester), ethylene glycol bis (3-mercaptoisobutanoic acid esters), propylene glycol two (3-mercaptoisobutanoic acid esters), glycol ether two (3-mercaptoisobutanoic acid esters), butyleneglycol two (3-mercaptoisobutanoic acid esters), ethohexadiol two (3-mercaptoisobutanoic acid esters), trimethylolpropane tris (3-mercaptoisobutanoic acid esters), tetramethylolmethane four (3-mercaptoisobutanoic acid esters), dipentaerythritol six (3-mercaptoisobutanoic acid esters), ethylene glycol bis (2-mercaptoisobutanoic acid esters), propylene glycol two (2-mercaptoisobutanoic acid esters), glycol ether two (2-mercaptoisobutanoic acid esters), butyleneglycol two (2-mercaptoisobutanoic acid esters), ethohexadiol two (2-mercaptoisobutanoic acid esters), trimethylolpropane tris (2-mercaptoisobutanoic acid esters), tetramethylolmethane four (2-mercaptoisobutanoic acid esters), dipentaerythritol six (2-mercaptoisobutanoic acid esters), ethylene glycol bis (4-mercaptopentanoic acid ester), propylene glycol two (4-sulfydryl isopentanoate), glycol ether two (4-mercaptopentanoic acid ester), butyleneglycol two (4-mercaptopentanoic acid ester), ethohexadiol two (4-mercaptopentanoic acid ester), trimethylolpropane tris (4-mercaptopentanoic acid ester), tetramethylolmethane four (4-mercaptopentanoic acid ester), dipentaerythritol six (4-mercaptopentanoic acid ester), ethylene glycol bis (3-mercaptopentanoic acid ester), propylene glycol two (3-mercaptopentanoic acid ester), glycol ether two (3-mercaptopentanoic acid ester), butyleneglycol two (3-mercaptopentanoic acid ester), ethohexadiol two (3-mercaptopentanoic acid ester), trimethylolpropane tris (3-mercaptopentanoic acid ester), tetramethylolmethane four (3-mercaptopentanoic acid ester), Dipentaerythritol six (3-mercaptopentanoic acid ester), Hydrogenated Bisphenol A two (3-mercaptobutylate), dihydroxyphenyl propane dihydroxy ethyl ether-3-mercaptobutylate, 4,4 '-(9-fluorenes fork base) two (2-Phenoxyethyl (3-mercaptobutylate)), ethylene glycol bis (3-sulfydryl-3-phenylpropionic acid ester), propylene glycol two (3-sulfydryl-3-phenylpropionic acid ester), glycol ether two (3-sulfydryl-3-phenylpropionic acid ester), butyleneglycol two (3-sulfydryl-3-phenylpropionic acid ester), ethohexadiol two (3-sulfydryl-3-phenylpropionic acid ester), trimethylolpropane tris (3-sulfydryl-3-phenylpropionic acid ester), three-2-(3-sulfydryl-3-phenylpropionic acid ester) ethyl isocyanurate, tetramethylolmethane four (3-sulfydryl-3-phenylpropionic acid ester), dipentaerythritol six (3-sulfydryl-3-phenylpropionic acid ester), ethylene glycol bis mercaptoacetate), 1,3-PD two (mercaptoacetate), propylene glycol two (mercaptoacetate), 1,3 butylene glycol two (mercaptoacetate), BDO two (mercaptoacetate), neopentyl glycol two (mercaptoacetate), 1,6-hexylene glycol two (mercaptoacetate), 1,8-ethohexadiol two (mercaptoacetate), 1,9-nonanediol two (mercaptoacetate), hexanaphthene-Isosorbide-5-Nitrae-dimethanol two (mercaptoacetate), glycol ether two (mercaptoacetate), triglycol two (mercaptoacetate), polyoxyethylene glycol two (mercaptoacetate), dipropylene glycol two (mercaptoacetate), tripropylene glycol two (mercaptoacetate), polypropylene glycol two (mercaptoacetate), polytetramethylene ether diol two (mercaptoacetate), two (mercaptoacetate) of hexanaphthene-Isosorbide-5-Nitrae-dimethanol ethylene oxide adduct, two (mercaptoacetate) of hydrogenated bisphenol A epoxy ethane additive product, two (mercaptoacetate) of hexanaphthene-Isosorbide-5-Nitrae-dimethanol propylene oxide adduct, two (mercaptoacetate) of hydrogenated bisphenol A epoxy propane affixture, glycerine three (mercaptoacetate), two glycerine four (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), one contracting two (TriMethylolPropane(TMP)) four (mercaptoacetate), tetramethylolmethane four (mercaptoacetate), dipentaerythritol six (mercaptoacetate), ethylene glycol bis (3-mercaptopropionic acid ester), 1,3-PD two (3-mercaptopropionic acid ester), propylene glycol two (3-mercaptopropionic acid ester), 1,3 butylene glycol two (3-mercaptopropionic acid ester), BDO two (3-mercaptopropionic acid ester), neopentyl glycol two (3-mercaptopropionic acid ester), 1,6-hexylene glycol two (3-mercaptopropionic acid ester), 1,8-ethohexadiol two (3-mercaptopropionic acid ester), 1,9-nonanediol two (3-mercaptopropionic acid ester), hexanaphthene-Isosorbide-5-Nitrae-dimethanol two (3-mercaptopropionic acid ester), glycol ether two (3-mercaptopropionic acid ester), triglycol two (3-mercaptopropionic acid ester), polyoxyethylene glycol two (3-mercaptopropionic acid ester), dipropylene glycol two (3-mercaptopropionic acid ester), tripropylene glycol two (3-mercaptopropionic acid ester), polypropylene glycol two (3-mercaptopropionic acid ester), polytetramethylene ether diol two (3-mercaptopropionic acid ester), two (the 3-mercaptopropionic acid ester) of hexanaphthene-Isosorbide-5-Nitrae-dimethanol ethylene oxide adduct, two (the 3-mercaptopropionic acid ester) of hydrogenated bisphenol A epoxy ethane additive product, two (the 3-mercaptopropionic acid ester) of hexanaphthene-Isosorbide-5-Nitrae-dimethanol propylene oxide adduct, two (the 3-mercaptopropionic acid ester) of hydrogenated bisphenol A epoxy propane affixture, glycerine three (3-mercaptopropionic acid ester), two glycerine four (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), one contracting two (TriMethylolPropane(TMP)) four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester) etc.
In these multi-thioalcohol compounds, preferably many (3-mercaptobutylate) body, particularly preferably polyoxyethylene glycol two (3-mercaptobutylate), tetramethylolmethane four (3-mercaptobutylate), dipentaerythritol six (3-mercaptobutylate) etc.And then, the structure of the concrete example of preferred multi-thioalcohol compound is below shown.
(in formula, n is the integer of 1 ~ 10.)
As preferred multi-thioalcohol compound, the compound with secondary sulfydryl can be enumerated.Himself package stability excellence compared with uncle's mercaptan compound of secondary mercaptan compound.In addition, the sealing material using light solidified sealing material of the present invention to generate has the sealing characteristics of light solidified sealing material excellence known than ever, but when use has the multi-thioalcohol compound of secondary mercaptan, coating stability during coating and the excellent in stability of sealing characteristics.Particularly stably can obtain the characteristic about hardness and flexibility excellence.As its reason, supposition is such as utilize thiol group periphery sterically hindered, the balance of the free radical reaction in alkene-thiol reactant and thermal addition reaction is adjusted well.
As the usage quantity of multi-thioalcohol compound, for (A) have the oligopolymer of (methyl) acryl and (B) (methyl) acrylate monomer both in contained (methyl) acryl and (C) multi-thioalcohol compound sulfydryl, the ratio of number that exists in light solidified sealing material becomes 100:5n ~ 100:25n (n is the number of the sulfydryl in multi-thioalcohol compound 1 molecule.) amount, preferably, can be enumerated this than the amount becoming 100:7n ~ 100:20n, more preferably, can be enumerated this than the amount becoming 100:9n ~ 100:17n.
(D) carbodiimide compound
So-called carbodiimide compound, refers to hydroxyl by the hydrolysis by resins such as polyester being generated or carboxyl removing and suppresses the chain stabilizer against hydrolysis (hydrolysis agent) that is hydrolyzed.As carbodiimide compound, can enumerate single carbodiimide compound and poly-carbodiimide compound etc., generally well-known, they all can use.Carbodiimide compound, can enumerate the compound recorded in such as Unexamined Patent 9-309871, Unexamined Patent 9-249801, Unexamined Patent 9-208649, Unexamined Patent 9-296097, Unexamined Patent 8-81533, Unexamined Patent 8-27092, Unexamined Patent 9-136869, Unexamined Patent 9-124582, Unexamined Patent 9-188807, JP 2005-82642, JP 2005-53870, JP 2012-36392, JP 2010-163203, JP 2011-174094, WO2008/072514, JP 2012-81759, JP 2012-52014, JP 2012-7079 etc.
Such as formula can be enumerated: R 12-(-N=C=N-R 11-) m-R 13
[in formula, R 11identical or different, be aromatic group and/or the aliphatic group of divalent.
When aromatic oligomer carbodiimide or aromatic polymer carbodiimide, R 11the aliphatic substitution of at least 1 carbon atom and/or ester ring type substituting group and/or aromatic substituents can be had replace.Wherein, these substituting groups can have heteroatoms, and in addition, these substituting groups can replace at the ortho position of at least 1 of the aromatic group of above-mentioned carbodiimide bonding.
R 12for C 1~ C 18alkyl, C 5~ C 18cycloalkyl, aryl, C 7~ C 18aralkyl ,-R 11-NH-COS-R 14,-R 11cOOR 14,-R 11-OR 14,-R 11-N (R 14) 2,-R 11-SR 14,-R 11-OH, R 11-NH 2,-R 11-NHR 14,-R 11-epoxy ,-R 11-NCO ,-R 11-NHCONHR 14,-R 11-NHCONR 14r 15or-R 11-NHCOOR 16.
R 13for-N=C=N-aryl ,-N=C=N-alkyl ,-N=C=N-cycloalkyl ,-N=C=N-aralkyl ,-NCO ,-NHCONHR 14,-NHCONHR 14r 15,-NHCOOR 16,-NHCOS-R 14,-COOR 14,-OR 14, epoxy ,-N (R 14) 2,-SR 14,-OH ,-NH 2,-NHR 14.
R 14and R 15identical or different, be C 1~ C 20alkyl, C 3~ C 20cycloalkyl, C 7~ C 18aralkyl, oligomeric/polyethylene glycols and/or oligomeric/polypropylene glycols.
R 16there is R 141 defined above, or be polyester based or polyamide-based.
When oligopolymer carbodiimide, m is 1 ~ 5.
When polymkeric substance carbodiimide, m is the integer larger than 5.] shown in compound.
As preferred carbodiimide compound, the fatty family with multiple-N=C=N-can be enumerated and gather carbodiimide compound, more preferably, straight-chain aliphatics based polymer compound can be enumerated.Particularly, fatty family can be enumerated and gather carbodiimide compound (Nisshinbo ケ ミ カ Le (strain) system: エ ラ ス ト ス タ Block H01) etc.
As the usage quantity of carbodiimide compound, such as, there is relative to (A) oligopolymer 100 weight part of (methyl) acryl; the scope of 0.1 ~ 15 weight part can be enumerated, preferably, 0.5 ~ 12 weight part can be enumerated; more preferably, 1 ~ 10 weight part can be enumerated.
As recorded in embodiment 9 ~ 11 described later, when the light solidified sealing material described in above-mentioned [1] is stored at 23 DEG C, within 1 month, stablize, but gelation thereafter.When with the addition of carbodiimide compound in this material, within more than 6 months, stablize, there is excellent package stability.In addition, on the physical property of the sealing material that light solidified and photocuring generate also almost without affecting.The present inventor infers, carry out and gelation in storage relative to the reaction of active sulphur alcohol radical contained in alkene-mercaptan system light-cured resin material and double bond, carbodiimide compound override and active thiol group and make its deactivation, thus create the shelf-stable effect produced by carbodiimide compound.Further, the effect that carbodiimide compound has the package stability of raising alkene-mercaptan system light-cured resin material is unknown so far, this effect is not easily to expect for those skilled in the art.
Above-mentioned carbodiimide compound also can use as the stabilization agent for alkene-mercaptan system light-cured resin material.As alkene-mercaptan system light solidified sealing material, comprise usually known material, the light-cured resin material etc. recorded in the alkene-mercaptan system light solidified sealing material and patent documentation 3 ~ 8 recorded in such as above-mentioned [1] can be enumerated.As the amount of the carbodiimide compound added in alkene-mercaptan system light-cured resin material, with reference to the amount used relative to the alkene recorded in above-mentioned [1]-mercaptan system light solidified sealing material, suitably can change and use.
(E) optical free radical polymerization starter
As optical free radical polymerization starter, the optical free radical polymerization starter of such as molecule internal fissure type and/or hydrogen-abstraction can be used, preferably enumerate molecule internal fissure type optical free radical polymerization starter.As the ultraviolet polymerization initiator of free radical, can suitably use known compound, particularly, bitter almond oil camphor class and these the alkyl ethers such as bitter almond oil camphor, benzoin methyl ether, benzoin ethyl ether can be enumerated; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 4-(the 1-tert-butyl dioxy-1-methylethyl) acetophenones such as methyl phenyl ketone, diethoxy acetophenone; The Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone; The thioxanthene ketones such as 2,4-dimethyl thioxanthone, 2,4-diisopropylthioxanthone, CTX; The ketal classes such as methyl phenyl ketone dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4-(1-tert-butyl dioxy-1-methylethyl) benzophenone, 3, the benzophenones such as 3 ', 4,4 '-four (tert-butyl dioxy carbonyl) benzophenone; 2-methyl isophthalic acid-alpha-aminoalkyl phenyl ketone such as [4-(methylthio group) phenyl]-2-morpholino-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone; 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxyl-1{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl } the Alpha-hydroxy alkyl phenyl ketones such as-2-methyl-propan-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone; The phenyl glyoxylic acid ester classes such as alkyl phenyl glyoxylic ester; Diethoxy acetophenone; The acylphosphine oxide classes such as 2,4,6-trimethylbenzoyl phenyl oxyethyl group phosphine oxide; Two cyclopentadiene titanium compounds such as two (5,2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base)-phenyl) titanium etc. and these combination of more than two kinds.
As preferred optical free radical polymerization starter, bitter almond oil camphor class, ketal class, Alpha-hydroxy alkyl phenyl ketones, alpha-aminoalkyl phenyl ketone, acylphosphine oxide class, phenyl glyoxylic acid ester class, acetophenones, two cyclopentadiene titanium compound equimolecular internal fissure type optical free radical initiators can be enumerated.
As the addition of optical free radical polymerization starter, there is no particular restriction, such as, relative to the gross weight 100 parts of each composition of (A) ~ (C), 0.1 ~ 10 weight part can be enumerated, preferably, 0.2 ~ 5 weight part can be enumerated, more preferably, 0.5 ~ 2 weight part can be enumerated.
(F) viscosity adjusting agent
As viscosity adjusting agent, be not particularly limited, white carbon black, colloidal silica, silica sand (ground silica), aerosil (ア エ ロ ジ Le), diatomite, hydrophobic calcium carbonate, glass hollow ball (ガ ラ ス バ ル ー Application), granulated glass sphere, Polyvinylpyrolidone (PVP) etc. can be enumerated.These viscosity adjusting agent can be used alone, and also two or more may be used.As preferred viscosity adjusting agent, the inorganic system viscosity adjusting agent such as aerosil can be enumerated.
As the addition of viscosity adjusting agent, there is no particular restriction, such as, relative to the gross weight 100 parts of each composition of (A) ~ (C), can enumerate 0.1 ~ 20 weight part, preferably enumerate 0.2 ~ 10 weight part.
(G) sensitizing agent
In order to not only use ultraviolet, even if use visible ray and near infrared ray also can photocuring, also sensitizing agent can be added.As sensitizing agent, can enumerate such as the polymethine pigment such as 1,2-derovatives such as the unsaturated ketone such as chalcone derivative, dibenzalacetone, camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivative, xanthene derivative, thioxanthene derivative, Xanthone derivative, thioxanthone derivates, coumarin derivatives, ketone coumarin derivatives, Cyanine derivative thing, Merocyanine derivatives, オ キ ソ ノ-Le derivative, acridine derivatives, azine derivatives, thiazine derivative, oxazine derivative, dihydroindole derivative, azulene derivatives, ア ズ レ ニ ウ system derivative, ス Network ア リ リ ウ system derivative, derivatives of porphyrin, Tetraphenyl porphyrin derivative, triarylmethane derivatives, Tetrabenzoporphyrin derivative, four pyrazines tetraazatetradecane porphyrin derivative, phthalocyanine derivates, four azepine tetraazatetradecane porphyrin derivatives, four quinoxalines tetraazatetradecane porphyrin derivative, naphthalene cyanines derivative, secondary phthalocyanine derivates, pyrans derivative, thiapyran derivative, テ ト ラ Off ィ リ Application derivative, wheel ene derivative, spiropyran derivatives, spiral shell oxazine derivative, spiral shell thiapyran derivative, metal-arene complex and organic ruthenium complex compound etc.
As the addition of sensitizing agent, there is no particular restriction, such as, relative to the gross weight 100 parts of each composition of (A) ~ (C), 0.1 ~ 10 weight part can be enumerated, preferably, 0.2 ~ 5 weight part can be enumerated, more preferably, 0.5 ~ 2 weight part can be enumerated.
other compositions
In light solidified sealing material of the present invention, other compositions can be added further.As other compositions, such as sensitizing agent, tackifier, stopper, pigment, adaptation rising agent, antioxidant, curing catalyst, weighting agent, softening agent, tensio-active agent, lubricant, static inhibitor etc. can be enumerated.These compositions according to each object, can add in right amount.
the modulation of light solidified sealing material
Light solidified sealing material of the present invention; can by being 10 by (A) weight-average molecular weight; 000 ~ 30; the oligopolymer with (methyl) acryl of 000, (B) (methyl) acrylate monomer, (C) multi-thioalcohol compound and optional (D) carbodiimide compound, (E) optical free radical polymerization starter, (F) sensitizing agent, (G) sensitizing agent and/or other compositions, under room temperature or heating condition, use the mixing machine mixing such as mixing machine, ball mill, 3 roller mixing rolls and modulate.In addition, also as required, can dissolve as thinner by adding solvent etc., mix and adjust.As the solvent being used as thinner, ketone, the tetrahydrofuran (THF)s, two such as ester, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone such as such as vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetate can be enumerated the halohydrocarbon such as aromatic hydrocarbons, methylene dichloride etc. such as the acid amides such as cyclic ether, DMF, toluene such as alkane.
the application method of light solidified sealing material
As the method making light solidified sealing material of the present invention solidify, there is no particular restriction, such as, can be implemented by irradiation energy line.As the energy line used, light, radioactive rays, hertzian wave etc. can be enumerated, particularly, ultraviolet, visible ray, infrared rays, alpha-ray, β ray, gamma-rays, electron beam etc. can be enumerated.From the view point of operability, productivity and economy etc., preferably use ultraviolet.As the irradiation time of energy line, suitably can select according to the kind of the energy line used.As ultraviolet light source, the light sources such as such as extra-high-pressure mercury vapour lamp, metal halide light, laser, LED can be used.When using alpha-ray, β ray, gamma-rays, electron beam etc., even if not containing optical free radical polymerization starter, also solidification promptly can be made to carry out, but under using ultraviolet situation, preferably optical free radical polymerization starter is added in light solidified sealing material of the present invention.
For situation light solidified sealing material of the present invention being applied to the packing ring in housing, be below described.When housing is made up of 2 parts clamping packing ring, according to the operation of following (1) ~ (4), housing of the present invention can be manufactured.
(1) groove (packing ring coating part) of the parts in one side is coated with light solidified sealing material equably;
(2) by this parts irradiation ultraviolet radiation etc. through coating, thus light solidified sealing material solidify, generation packing ring;
(3) inner device assembles will be contained in as required; With
(4) make the parts of the opposing party chimeric with these parts.
In the present invention, so-called " housing ", means wherein to be equipped with to have the equipment of certain function, the casing of electric installation, protects this equipment from the impact of impact, pressure, hertzian wave, water, dust, light etc.Particularly, the precision equipments etc. such as family's electrical article, photographic camera, clock and watch such as the electronic productses such as mobile telephone, digital camera, pick up camera, refrigerator, air-conditioning, washing machine can be enumerated.When sealing material of the present invention is used for housing, being mixed into of anti-sealing, pressure, dust etc., can not make the above-mentioned provide protection complete loss of housing.
the characteristic of sealing material
Sealing material of the present invention has high compression recovery rate, high tensile strength, excellent flexibility, has low hardness as required, and the sealing characteristics such as resistance to air loss, water-repellancy is excellent thus, and then surface viscosity is little.In addition, the hardness of the sealing material measured value meter adopting A type hardness tester meter, is preferably less than 40, is more preferably less than 30, and more preferably less than 20, be particularly preferably less than 15.In order to make its hardness step-down, by increasing the content of (B) (methyl) acrylate monomer and/or (C) multi-thioalcohol compound, can the hardness of adjustment aim.For these, illustrate in greater detail in an embodiment.
Embodiment
Below by way of reference example and embodiment to the detailed description of the invention.Further, these embodiments are only for the present invention will be described, there is not any restriction to the present invention.
[test method]
(1) tensile at break intensity, elongation
By the sheet material of the UV resin cured matter of thick 1mm, according to JIS K 6251, stamping-out is No. 3 type dumbbells, makes test film.Under the condition that test temperature 23 DEG C, draw speed 100m/ divide, carry out tension test, measure tensile at break intensity and elongation.
Breaking point tensile strength [MPa]=breaking tenacity/film sectional area
Elongation [%]=(extension at break amount/datum length [20mm]) × 100
(2) hardness
According to JIS K 6253, the thickness of stacked UV resin cured matter is about 1mm sheet material, and thickness becomes about 10mm, under 50 ~ 60%RH, uses A type hardness tester meter (polymer gauge system) to measure Durometer A hardness to this detection bodies in 23 DEG C.
(3) compression recovery
The stacked sheet material being cut into the square UV resin cured matter of 25mm, thickness becomes about 5mm, this detection bodies is carried out respectively 25% compression, 50% compression, according to JIS K 6253, under the condition of test temperature 70 DEG C, measures compression recovery.
(4) surface viscosity
After UV solidification, after the sheet material of the UV resin cured matter of thick 1mm is placed 2 hours in 23 DEG C, touched the viscosity evaluating irradiating surface by finger.Below evaluate.
Zero: roughly inviscid
△: slightly viscosity
×: there is strong viscosity
(5) package stability
Loaded by UV cured resin in the container of shading, place 2 weeks under 40 DEG C of environment after, whether acknowledgement state is unchanged.And use Brookfield viscometer to measure viscosity under 0.5rpm, to confirm compared with initial stage viscosity being the whether velocity of variation within 10%.
In addition, the package stability in table 3 is based on the viscosity after placing each time at each temperature and evaluates relative to the viscosity B coefficent of initial stage viscosity and change of state.
Zero: relative to initial stage viscosity, the velocity of variation within 10%
×: the generation of significant thickening and gelation
embodiment 1
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 8 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 2
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 23 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 3
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptopropionic acid ester) (SC organic chemistry (strain) system: PEMP) 17 weight parts of the molecular weight 488.64 of 4 officials' energy (primary) polythiol B, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 4
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 17 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 5
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as 1 of the molecular weight 567.7 of 3 officials' energy (second month in a season) polythiol C, 3, 5-tri-(3-sulfydryl butoxyethyl group)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, (Showa electrician (strain) makes 5H)-triketone: カ レ Application ズ MT NR1) 8 weight parts, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 6
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as 1 of the molecular weight 567.7 of 3 officials' energy (second month in a season) polythiol C, 3, 5-tri-(3-sulfydryl butoxyethyl group)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, (Showa electrician (strain) makes 5H)-triketone: カ レ Application ズ MT NR1) 12 weight parts, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 7
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as 1 of the molecular weight 294.4 of 2 officials' energy (second month in a season) polythiol D, (Showa electrician (strain) makes two (the 3-sulfydryl butyryl acyloxy) butane of 4-: カ レ Application ズ MT BD1) 9 weight parts, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
embodiment 8
By weight-average molecular weight 18, urethane acrylates system oligopolymer A (Japanese synthetic chemistry system: UV-3000B) 100 weight parts of 000, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as dipentaerythritol six (3-mercaptopropionic acid ester) (SC organic chemistry (strain) system: DPMP) 11 weight parts of the molecular weight 783.03 of 6 officials' energy (primary) polythiol E, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material of the present invention.
comparative example 1
By weight-average molecular weight 13, the urethane acrylates system oligopolymer A of 000 (make: KAYARAD UX-3204) 100 weight parts by Japanese chemical drug (strain), as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
comparative example 2
By weight-average molecular weight 13, the urethane acrylates system oligopolymer A of 000 (make: KAYARAD UX-3204) 100 weight parts by Japanese chemical drug (strain), as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 5 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
comparative example 3
By weight-average molecular weight 13, the urethane acrylates system oligopolymer A of 000 (make: KAYARAD UX-3204) 100 weight parts by Japanese chemical drug (strain), as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 38 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
comparative example 4
By weight-average molecular weight 4, (common prosperity society (strain) makes the urethane acrylates system oligopolymer B of 500: UF-8001G) 100 weight parts, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 7 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
comparative example 5
By weight-average molecular weight 4, (common prosperity society (strain) makes the urethane acrylates system oligopolymer B of 500: UF-8001G) 100 weight parts, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 17 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
comparative example 6
By weight-average molecular weight 4, (common prosperity society (strain) makes the urethane acrylates system oligopolymer B of 500: UF-8001G) 100 weight parts, as phenol acrylate (the first pharmaceutical industries (strain): ニ processed ュ ー Off ロ Application テ ィ ア PHE-2) 60 weight parts of acrylic monomer, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 23 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
comparative example 7
By weight-average molecular weight 4, (common prosperity society (strain) makes the urethane acrylates system oligopolymer B of 500: UF-8001G) 100 weight parts, as tetramethylolmethane four (3-mercaptobutylate) (Showa electrician (strain) system: カ レ Application ズ MT PE1) 4 weight parts of the molecular weight 544.8 of 4 officials' energy (second month in a season) polythiol A, viscosity adjusting agent (Japanese ア エ ロ ジ Le (strain) system: AEROSIL200) 8 weight part agitators are equably after vacuum mixing, add 1-hydroxy-cyclohexyl-phenyl-one (BASF ジ ャ パ Application (strain) system: イ Le ガ キ ュ ア 184) 2 weight parts as Photoepolymerizationinitiater initiater, as 1 of stablizer, 4-dihydroxy-benzene (Mitsui Chemicals (strain) is made: quinhydrones) 0.02 weight part, with the deaeration of agitator Homogeneous phase mixing, obtain light solidified sealing material.
test example 1
After each light solidified sealing material obtained in embodiment 1 ~ 8 and comparative example 1 ~ 7 is shaped to the sheet of thick about 1mm, use the electrodeless metal halide lamp-based UV irradiating unit (accumulated light of Tokyo ホ ト Application FOTOCURE TFL-150 base material-lamp spacing d=53mm, UV-A ripple: about 7000mJ/cm 2), carry out UV irradiation, make it solidify, modulate sealing material respectively.Accumulated light EIT society UV Power Pack measures.
For the sealing material obtained, above-mentioned test method is adopted to test physical property.Below record its result.
The sealing material of the present invention obtained in embodiment 1 ~ 8, compared with comparative example, has high compression recovery rate, high tensile strength, excellent flexibility and low hardness.In addition, by adding mercaptan, showing good adaptation and low surface viscosity, also showing good storage stability.
The experiment of comparative example 4 ~ 7 is done one's utmost to chase after examination approx with the experiment recorded in the table 2 for patent documentation 7, and are all extreme hardness, become more than 50, elongation is also low.In addition, in comparative example 6, in order to become soft as far as possible, the amount of mercaptan compound is added, even if but like this, hardness, also more than 50, can not be used as housing sealing material.
As shown in comparative example 1 and 2, when not add multi-thioalcohol compound and acryl/thiol group ratio be the addition of below 100/5n, hardness is high, does not obtain good flexibility, and elongation is also low.On the contrary, as shown in comparative example 3, add multi-thioalcohol compound until when acryl/thiol group ratio is more than 100/25n, do not obtain sufficient cohesive force, become the state that can not measure film physical property.
embodiment 9 ~ 11
In embodiment 4, add poly-carbodiimide compound (Nisshinbo ケ ミ カ Le (strain) system: エ ラ ス ト ス タ Block H01), obtain light solidified sealing material of the present invention of the amount recorded in following table 3.
[table 3]
Can be understood by this experiment, by adding carbodiimide compound, package stability significantly improves.Such as, when the light solidified sealing material of embodiment 4 is stored at 23 DEG C, within 1 month, stablize, but gelation thereafter.For the light solidified sealing material of embodiment 9 ~ 11 that with the addition of carbodiimide compound, within more than 6 months, stablize, there is excellent package stability.Further, the ceiling temperature when temperature of 23 DEG C is dark cold place preservation, the stability therefore at this temperature is equivalent to the package stability preserved at dark cold place.
Industry utilizes possibility
According to the present invention, provide and have high compression recovery rate, high tensile strength, excellent flexibility, have low hardness as required, the sealing characteristics such as resistance to air loss, water-repellancy is excellent thus, and the sealing material that surface viscosity is little.In addition, provide simple and easy and be cured to the deep of light solidified sealing material instantaneously and generate sealing material, there is the light solidified sealing material of package stability.

Claims (11)

1. light solidified sealing material; that to comprise (A) weight-average molecular weight be 10; 000 ~ 30; the light solidified sealing material of the oligopolymer with (methyl) acryl of 000, (B) (methyl) acrylate monomer and (C) multi-thioalcohol compound
There is relative to (A) oligopolymer 100 weight part of (methyl) acryl, comprise (B) (methyl) acrylate of 5 ~ 100 weight parts,
(A) have the oligopolymer of (methyl) acryl and (B) (methyl) acrylate monomer both in contained (methyl) acryl and (C) multi-thioalcohol compound sulfydryl, the number of the ratio of number that exists in the light solidified sealing material sulfydryl that to be 100:5n ~ 100:25n, n be in multi-thioalcohol compound 1 molecule.
2. light solidified sealing material according to claim 1, wherein, has oligopolymer 100 weight part of (methyl) acryl, also comprises (D) carbodiimide compound of 0.1 ~ 15 weight part relative to (A).
3. the light solidified sealing material described in claim 1 or 2, wherein, (C) multi-thioalcohol compound has 2 ~ 6 sulfydryls in 1 molecule, and its sulfydryl is secondary sulfydryl.
4. the light solidified sealing material described in claim 1 or 2, wherein, (C) multi-thioalcohol compound is the ester generated by the polyvalent alcohol and β-mercaptobutyric acid with 2 ~ 6 hydroxyls.
5. the light solidified sealing material described in any one of Claims 1 to 4, wherein, (B) (methyl) acrylate monomer is simple function (methyl) acrylate, multifunctional (methyl) acrylate or these combination.
6. the light solidified sealing material described in any one of Claims 1 to 5; wherein, (A) has the oligopolymer of (methyl) acryl is at least a kind that selects from the group comprising carbamate system (methyl) origoester acrylate, Polyester (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy (methyl) origoester acrylate, conjugated diolefin polymer system (methyl) origoester acrylate and these hydride.
7. the light solidified sealing material described in any one of claim 1 ~ 6, wherein, also comprises (E) optical free radical polymerization starter and/or (F) viscosity adjusting agent.
8. sealing method, it is undertaken by making the light solidified sealing material described in any one of claim 1 ~ 7 carry out photocuring.
9. sealing material, it generates by making the light solidified sealing material described in any one of claim 1 ~ 7 carry out photocuring.
10. housing, it uses the sealing material generated by making the light solidified sealing material described in any one of claim 1 ~ 7 carry out photocuring.
11. for the stabilization agent of alkene-mercaptan system light-cured resin material, and it contains carbodiimide compound.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016021531A1 (en) * 2014-08-04 2017-05-18 積水化学工業株式会社 Sealant for display element
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WO2023167067A1 (en) * 2022-03-01 2023-09-07 パナソニックＩｐマネジメント株式会社 Curable composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010126040A1 (en) * 2009-04-27 2010-11-04 株式会社ブリヂストン Energy-ray-curable elastomer composition, material for gasket, gasket, and hard disk device
CN103958637A (en) * 2011-11-29 2014-07-30 新田明胶株式会社 Material for photocurable sealing, sealing method, sealing material, and case using same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4813940B1 (en) * 1969-01-24 1973-05-01
DE10126149A1 (en) * 2001-05-30 2002-12-05 Mitsubishi Polyester Film Gmbh Opaque colored, hydrolysis-resistant, biaxially oriented film made of a crystallizable thermoplastic and process for its production
JP4112961B2 (en) * 2002-12-06 2008-07-02 東レ株式会社 Polyester monofilament and industrial fabric
JP2006321933A (en) * 2005-05-20 2006-11-30 Teijin Ltd Polyethylene naphthalene resin composition and method for producing the same
JP2008255214A (en) * 2007-04-04 2008-10-23 Teijin Chem Ltd Aromatic polycarbonate resin composition
JP2009141808A (en) * 2007-12-07 2009-06-25 Bridgestone Corp Curable damping material for speaker edge
JP5329826B2 (en) * 2008-03-03 2013-10-30 ユニチカ株式会社 Biodegradable polyester resin composition and molded article comprising the same
JP2010254854A (en) * 2009-04-27 2010-11-11 Bridgestone Corp Energy ray curing type elastomer composition
JP5649292B2 (en) * 2009-08-25 2015-01-07 株式会社ブリヂストン Energy ray curable elastomer composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010126040A1 (en) * 2009-04-27 2010-11-04 株式会社ブリヂストン Energy-ray-curable elastomer composition, material for gasket, gasket, and hard disk device
CN103958637A (en) * 2011-11-29 2014-07-30 新田明胶株式会社 Material for photocurable sealing, sealing method, sealing material, and case using same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106749938A (en) * 2015-11-20 2017-05-31 财团法人工业技术研究院 Packaging composition and packaging structure comprising same
CN106749938B (en) * 2015-11-20 2019-10-01 财团法人工业技术研究院 Packaging composition and packaging structure comprising same
CN111699234A (en) * 2018-01-23 2020-09-22 博斯蒂克股份公司 Photocurable sealing material
TWI712681B (en) * 2018-01-23 2020-12-11 法商波士提克公司 Light-curing sealing material
US11130891B2 (en) 2018-01-23 2021-09-28 Bostik Sa Photocurable sealing material
CN112745770A (en) * 2019-10-31 2021-05-04 味之素株式会社 Curable composition
CN112745770B (en) * 2019-10-31 2024-08-02 味之素株式会社 Curable composition

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