CN103764701A - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
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- CN103764701A CN103764701A CN201280041431.1A CN201280041431A CN103764701A CN 103764701 A CN103764701 A CN 103764701A CN 201280041431 A CN201280041431 A CN 201280041431A CN 103764701 A CN103764701 A CN 103764701A
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- methyl
- acrylate
- curable resin
- resin composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
Abstract
Provided is a curable resin composition exhibiting high adhesion durability. The curable resin composition contains: a (meth)acrylate oligomer (A) selected from the group consisting of urethane-based (meth)acrylate oligomers, polyester-based (meth)acrylate oligomers, polyether-based (meth)acrylate oligomers, epoxy-based (meth)acrylate oligomers, diene polymer-based (meth)acrylate oligomers, and oligomers having a backbone of the hydrogenated product of a diene polymer-based (meth)acrylate; a (meth)acrylate (B) exhibiting a homopolymer glass transition temperature of -100 DEG C to 60 DEG C; one or more compounds (C) having one mercapto group per molecule, the compound(s) being selected from the group consisting of alkanethiols and carboxythiols; and a photopolymerization initiator (D).
Description
Technical field
The present invention relates to curable resin composition.
Background technology
The touch panel carrying on the indicating meters such as LCD has resistance membrane type, condenser type, induction, optical profile type etc.On these touch panels, be sometimes fitted with for making the good decorative sheet of the designability of outward appearance, specify the icon sheet (icon sheet) of touch location.Capacitive touch panels has and on transparency carrier, forms transparency electrode, the structure that the transparent panel of fitting forms thereon.
In recent years the glass attenuation just gradually of the indicating meter such as LCD.During glass attenuation, the externally LCD easily distortion that becomes under stress.When by optical functional materials laminatings such as the indicating meters such as the LCD of this thin glass and acrylic board, polycarbonate plates, strain during due to the moulding of the plastic shaping materials such as different, the acrylic board of the polar expansion of glass and acrylic board etc., polycarbonate, in oven test, humidity test, cause mitigation, the moisture absorption/dry of moulding strain, occur that the surface accuracies such as dimensional change, warpage change.While wanting for example, to suppress this distortion with existing caking agent (patent documentation 1), exist bonding plane to peel off, LCD splits or LCD shows inhomogeneous and so on problem.
As the solution countermeasure of such problem, there is the such UV gel-type resin of patent documentation 2.
In addition, in the purposes such as laminating of the laminating of laminating, icon sheet and the touch panel of decorative sheet and touch panel, the transparency carrier that is formed with transparency electrode in capacitive touch panels and transparent panel, expectation has the flexibility of the degree of the distortion that can follow adherend under the environment of heating of supposition environment for use.As the means of giving flexibility, such just like patent documentation 3, take diene polymer and there is the curable resin composition that the compound of 2 sulfydryls is essential component.In addition, as the material that contains the compound with sulfydryl, there are patent documentation 4, the such curable resin composition of patent documentation 5.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-77887 communique
Patent documentation 2: Japanese kokai publication sho 64-85209 communique
Patent documentation 3: TOHKEMY 2009-256465 communique
Patent documentation 4: No. 2010/027041 brochure of International Publication
Patent documentation 5: TOHKEMY 2011-26492 communique
Summary of the invention
the problem that invention will solve
Yet think, because the UV gel-type resin of above-mentioned patent documentation 2 is basic snappiness resin for take the skeleton monomer of the such rigidity of (methyl) isobornyl acrylate, so in high temperature reliability test, peel off thereby the dilation that can not adapt to adherend produces.
In addition, the inventor etc. have confirmed, use select the compound in a kind of above molecule in the group that free alkanethiol and carboxyl mercaptan forms with 1 sulfydryl as a composition of curable resin composition there is the compound of sulfydryl time, can access the curable resin composition (for example, with reference to embodiment described later) of high adhesion durability.On the other hand, think in above-mentioned patent documentation 3～5, owing to not using the compound with sulfydryl of such particular types, so can not control flexibility, cementability of curable resin composition etc.
The object of the present invention is to provide a kind of curable resin composition, it can solve such as in laminating during for the decorative sheet of the indicating meters such as touch panel, icon sheet, in being fitted in capacitance touch panel be formed with the transparency carrier of transparency electrode time, when laminating is printed part, be difficult to give the problem of the such prior art of sufficient cementability, or bonding plane is peeled off or the split problem of such prior art of the glass of indicating meter when laminating indicating meter and optical functional materials.
for the scheme of dealing with problems
, according to the present invention, a kind of curable resin composition is provided, it contains: (A) select free polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy system (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate, and a kind of above (methyl) origoester acrylate in the group that forms of the oligopolymer of skeleton with the hydrogenation thing of diene polymerization system (methyl) acrylate, (B) homopolymer glass transition temperature is (methyl) acrylate of-100～60 ℃, (C) select the compound in a kind of above molecule in the group that free alkanethiol and carboxyl mercaptan forms with 1 sulfydryl, and (D) Photoepolymerizationinitiater initiater.
In addition, according to the present invention, provide a kind of curable resin composition, in above-mentioned curable resin composition, also contain above-mentioned (A) and (B) (methyl) acrylate in addition as (E) composition.In addition, according to the present invention, provide a kind of curable resin composition, wherein, above-mentioned (E) composition is trimethylolpropane tris (methyl) acrylate and/or tristane dimethanol (methyl) acrylate.In addition, according to the present invention, provide a kind of curable resin composition, wherein, the compound that the molecule of above-mentioned (C) contains 1 sulfydryl is the alkanethiol shown in following formula (1).
C
nh
2n+1sH formula (1)
(integer that n is 4～19)
In addition, according to the present invention, provide this curable resin composition, wherein, the compound that molecule (C) contains 1 sulfydryl is the carboxyl mercaptan shown in following formula (2).
ROOC(CH
2)
psH formula (2)
(R is the alkyl of hydrogen or carbon number 1～19, and p is integer)
In addition, according to the present invention, provide a kind of curable resin composition, wherein, the weight-average molecular weight of above-mentioned (A) composition is 500～100000.In addition, according to the present invention, provide a kind of curable resin composition, wherein, the number-average molecular weight of above-mentioned (A) composition is 500～100000.In addition, according to the present invention, provide a kind of adhesive composite, it comprises above-mentioned curable resin composition.In addition, according to the present invention, provide a kind of cured body of above-mentioned adhesive composite.In addition, according to the present invention, provide a species complex, it is by above-mentioned cured body, adherend to be covered or engaged to form.In addition, according to the present invention, provide a species complex, wherein, above-mentioned adherend be select in the group that free cellulosetri-acetate, fluorine based polymer, polyester, polycarbonate, polyolefine, glass and metal form more than a kind.In addition, according to the present invention, provide a kind of touch panel duplexer, it is by above-mentioned adhesive composite, adherend laminating to be formed.In addition, according to the present invention, provide a kind of liquid crystal panel duplexer, it is by above-mentioned adhesive composite, adherend laminating to be formed.In addition, according to the present invention, provide a kind of indicating meter, it has used above-mentioned touch panel duplexer.In addition, according to the present invention, provide a kind of indicating meter, it has used above-mentioned liquid crystal panel duplexer.
the effect of invention
Curable resin composition of the present invention shows high adhesion durability.
Embodiment
Below embodiments of the present invention are elaborated.
Multifunctional (methyl) acrylate refers to (methyl) acrylate that includes more than 2 (methyl) acryl in 1 molecule.Simple function (methyl) acrylate comprises 1 (methyl) acryl (methyl) acrylate in 1 molecule.
((A) composition: polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy are the oligopolymer of the skeleton of (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate and the hydrogenation thing with diene polymerization system (methyl) acrylate)
Oligopolymer as (A) composition, preferably has the liquid-state oligomers of (methyl) acryl.As this liquid-state oligomers, from the viewpoint of solidified nature, can preferably use the oligopolymer in molecule with at least 2 (methyl) acryls.The number of (methyl) acryl in 1 molecule is preferably 2～6, more preferably 2～4, most preferably is 2.(methyl) acryl can be positioned at two ends or single end of the oligopolymer of (A) composition.(methyl) acryl refers to acryl or methacryloyl.
As the oligopolymer with (methyl) acryl; have no particular limits, such as listing: select free polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy system's (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate and there is a kind of above (methyl) origoester acrylate in the group that the oligopolymer of skeleton of the hydrogenation thing of diene polymerization system (methyl) acrylate forms etc.
To thering is the main chain backbone of the oligopolymer of (methyl) acryl, have no particular limits, for example, can be: be selected from hydrogenation thing, the polyisoprene of polyhutadiene, polyhutadiene, in hydrogenation thing, polyester, dibutylene glycol, polycarbonate and the polyethers of polyisoprene more than a kind.
Polyurethane series (methyl) origoester acrylate refers to (methyl) origoester acrylate in molecule for example with amino-formate bond.Polyurethane series (methyl) origoester acrylate can by such as to the urethane oligomer that polybutadiene diol, polyether glycol, polyester polyol, polycarbonate diol etc. is reacted with polyisocyanates obtain with (methyl) thus vinylformic acid carries out esterification to be obtained.Polyhutadiene is carried out to (methyl) polybutadiene-modified polyurethane series (methyl) acrylate acrylic acid modified and that obtain to be also contained in polyurethane series (methyl) origoester acrylate.The polyhutadiene of hydrogenation is carried out to (methyl) hydrogenation polybutadiene-modified polyurethane series (methyl) acrylate acrylic acid modified and that obtain to be also contained in polyurethane series (methyl) origoester acrylate.As polyurethane series (methyl) origoester acrylate, can list: 1,2-polybutadiene-modified polyurethane series (methyl) origoester acrylate, polyester-polyurethane system (methyl) origoester acrylate, dibutylene glycol polyurethane series (methyl) origoester acrylate, polycarbonate polyurethane system (methyl) origoester acrylate, polyether-polyurethane system (methyl) origoester acrylate etc.
Polyester system (methyl) origoester acrylate can carry out by hydroxyl use (methyl) vinylformic acid that there is the polyester oligomer of hydroxyl at two the ends for example condensation by polycarboxylic acid and polyvalent alcohol being obtained esterification or to the hydroxyl of end that makes the oligopolymer that polycarboxylic acid addition epoxy alkane obtains with (methyl) thus vinylformic acid carries out esterification to be obtained.
Polyethers system (methyl) origoester acrylate can by for example to the hydroxyl of polyether glycol with (methyl) thus vinylformic acid carries out esterification to be obtained.
Epoxy system (methyl) origoester acrylate can be by for example making the bisphenol-type epoxy resin of lower molecular weight, the oxyethane ring of phenolic resin varnish type epoxy resin with (methyl) thus vinylformic acid reacts, esterification obtains.In addition, also can use this epoxy system (methyl) origoester acrylate is carried out to carboxy-modified type epoxy partially modified and that obtain system (methyl) origoester acrylate with dicarboxylic acid anhydride.
As diene polymerization system (methyl) origoester acrylate, such as listing: liquid towards styrene-butadiene copolymer carries out (methyl) acrylic acid modified and SBR bis-(methyl) acrylate of obtaining, polyisoprene is carried out to (methyl) acrylic acid modified and polyisoprene two (methyl) acrylate of obtaining etc.
Have diene polymerization system (methyl) acrylate hydrogenation thing skeleton oligopolymer can by for example to thering is hydroxyl hydroxyl, hydrogenation polyhutadiene or hydrogenation polyisoprene at two ends with (methyl) thus vinylformic acid carries out esterification to be obtained.
In present embodiment, the above-mentioned liquid-state oligomers with (methyl) acryl can be used singly or in combination of two or more.Among liquid-state oligomers, from the viewpoint of solidified nature etc., optimization polyurethane system (methyl) origoester acrylate, more preferably 2 functional polyurethanes system (methyl) origoester acrylates.2 functional polyurethanes systems (methyl) origoester acrylates refer in 1 molecule of polyurethane series (methyl) origoester acrylate and comprise 2 (methyl) acryls.
2 functional polyurethanes systems (methyl) origoester acrylates can by urethane oligomer with (methyl) thus vinylformic acid carries out esterification to be obtained.Urethane oligomer can be by thering are 2 hydroxyls in molecule polyether glycol, polyester polyol, polycarbonate diol etc. obtain with reacting of polyisocyanates.
As the polyether glycol with 2 hydroxyls, for example can use: polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol (polytetramethylene glycol), polyhexamethylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, neopentyl glycol, cyclohexanedimethanol, 2, the additions such as two (4-hydroxy-cyclohexyl) propane of 2-, dihydroxyphenyl propane oxyethane or propylene oxide etc. and the compound that obtains etc.
The polyester polyol with 2 hydroxyls, can be by for example making alcohol composition react and obtain with sour composition.The polyester polyol with 2 hydroxyls can for example pass through: with polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol (polytetramethylene glycol), 1, 3-butyleneglycol, 1, 4-butyleneglycol, 1, 6-hexylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, 2, two (4-hydroxy-cyclohexyl) propane of 2-, the additions such as dihydroxyphenyl propane oxyethane or propylene oxide etc. and the compound that obtains, or addition 6-caprolactone and the compound that obtains etc. are alcohol composition, with hexanodioic acid, sebacic acid, nonane diacid, the diprotic acid such as dodecanedioic acid and acid anhydrides thereof are sour composition, make alcohol composition react and use with sour composition.By the compound that this three's simultaneous reactions of above-mentioned alcohol composition, sour composition and 6-caprolactone is obtained, also can be used as polyester polyol uses.
Weight-average molecular weight, the number-average molecular weight of polyurethane series (methyl) origoester acrylate, from viewpoints such as treatability, be preferably 500～100000, and more preferably 1000～50000.To this value, there is no particular limitation, for example, can be 500,1000,2000,3000,4000,5000,7000,10000,20000,30000,40000,50000 or 100000, also can the scope in arbitrary value wherein in.The value that molecular-weight average converts for the polystyrene standard of measuring by gel permeation chromatography (GPC) method.Particularly, molecular-weight average under following condition, use tetrahydrofuran (THF) as solvent, use GPC system (SC-8010 that TOSOH CORPORATION manufactures), with commercially available polystyrene standard, make typical curve and obtain.
Flow velocity: 1.0ml/min
Design temperature: 40 ℃
Post forms: 1 TOSOH CORPORATION manufacture " TSK guardcolumn MP(* L) " 6.0mmID * 4.0cm and 2 " TSK-GELMULTIPOREHXL-M " 7.8mmID * 30.0cm(theoretical plate numbers 16 that TOSOH CORPORATION manufactures, 000 column plate), count 3 (global theory stage number 32,000 column plates);
Sample injection rate: 100 μ l(test liquid concentration 1mg/ml)
Liquor charging pressure: 39kg/cm
2
Detector: RI detector
Polyurethane series in present embodiment (methyl) origoester acrylate can be also the material that for example following general formula (1) represents.
(R' of general formula is H or CH
3)
Wherein, also can replace butadiene structure as follows,
Select the as follows structure that butadiene hydrogenation is obtained.
It should be noted that, in above-mentioned general formula (1), R' is CH
3compound, compound or the R' that R' is H be H and replace butadiene structure as implied above to select the compound of the as implied above structure that butadiene hydrogenation is obtained, for example can buy (trade mark is followed successively by TE-2000, TEA-1000, TEAI-1000) from Japanese Cao Da company.
((B) composition: homopolymer glass transition temperature is (methyl) acrylate of-100～60 ℃)
It as homopolymer glass transition temperature, is (methyl) acrylate of-100～60 ℃, can list: (methyl) lauryl acrylate (homopolymer glass transition temperature of acrylate :-30 ℃, the homopolymer glass transition temperature of methacrylic ester :-65 ℃), (methyl) ethyl acrylate (homopolymer glass transition temperature of acrylate :-85 ℃, the homopolymer glass transition temperature of methacrylic ester :-10 ℃), (methyl) n-butyl acrylate (homopolymer glass transition temperature of methacrylic ester: 20 ℃), (methyl) isobutyl acrylate (homopolymer glass transition temperature of methacrylic ester: 20 ℃), (methyl) tert-butyl acrylate (homopolymer glass transition temperature of methacrylic ester: 20 ℃), (methyl) vinylformic acid methoxyl group ethyl ester (homopolymer glass transition temperature of acrylate :-50 ℃), two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid-1, 3-butanediol ester, dicyclopentenyl oxygen base ethyl (methyl) acrylate (Dicyclopentenyloxyethyl(meth) acrylate) (homopolymer glass transition temperature: 25 ℃), (methyl) 2-Hydroxy ethyl acrylate (homopolymer glass transition temperature of methacrylic ester: 55 ℃), (methyl) 2-hydroxypropyl acrylate (homopolymer glass transition temperature of acrylate :-7 ℃, the homopolymer glass transition temperature of methacrylic ester: 26 ℃), (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester (homopolymer glass transition temperature of acrylate :-80 ℃), (methyl) Isooctyl acrylate monomer (homopolymer glass transition temperature of acrylate :-58 ℃, the homopolymer glass transition temperature of methacrylic ester :-30 ℃), the different stearyl ester of (methyl) vinylformic acid (homopolymer glass transition temperature of acrylate :-18 ℃, the homopolymer glass transition temperature of methacrylic ester: 30 ℃), (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems (homopolymer glass transition temperature of acrylate :-58 ℃, the homopolymer glass transition temperature of methacrylic ester :-30 ℃), (methyl) vinylformic acid Nonylphenoxy polyoxyethylene glycol (has-(CH
2cH
2o)
n-structure, n=1～17) ester (homopolymer glass transition temperature :-25～20 ℃), vinylformic acid phenoxy group glycol ester (homopolymer glass transition temperature :-25～30 ℃) etc.These (methyl) acrylate can be used one kind or two or more.Above-mentioned-100～60 ℃ can be for for example :-100 ,-90 ,-80 ,-70 ,-60 ,-50 ,-40 ,-30 ,-20 ,-10,0,10,20,30,40,50 or 60 ℃, also can the scope in arbitrary value wherein in.
Glass transition refers to that at high temperature materials such as glass for liquid are because temperature reduces, and in certain temperature range, its viscosity sharply increases, almost lost flowability and become the variation of amorphous solid.As the measuring method of second-order transition temperature, there is no particular limitation, generally refers to the second-order transition temperature of calculating by thermogravimetric flow measurement, means of differential scanning calorimetry mensuration, differential thermal mensuration, Measurement of Dynamic Viscoelasticity.Wherein, preferred Measurement of Dynamic Viscoelasticity.
The second-order transition temperature of the homopolymer of (methyl) acrylate is recorded in J.Brandrup, E.H.Immergut, Polymer Handbook, 2nd Ed., J.Wiley, in New York1975, photocuring technology databook (TECHNONET.Co., Ltd) etc.
These homopolymer glass transition temperature are among the ultra-violet solidified compound of-100～60 ℃, from the large viewpoint of cementability, and the compound of preferred formula (2).
General formula (2) Z-O-R
1
(in formula, Z represents (methyl) acryl, R
1represent to have the functional group of aromatic ring or the alkyl that carbon number is 9～20.〕
The compound of general formula (2) further improves the flexibility of cured article, and the adaptation of cured article and polyethylene terephthalate etc. is further improved.As the compound of general formula (2), can list: (methyl) acrylic acid ester with aromatic rings such as nonyl phenyl, Nonylphenoxy polyethylene glycol groups, phenoxy group, phenoxy group ethylene glycols; Having the carbon numbers such as nonyl, different nonyl, decyl, isodecyl, dodecyl, lauryl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl is (methyl) acrylic acid ester of the alkyl of 9～20.Among these, preferably carbon number is the alkyl of the straight or branched of 9～20, and more preferably carbon number is the alkyl of 10～16, and most preferably carbon number is the alkyl of 11～14, be preferably selected from the group being formed by lauryl and iso stearyl more than a kind.These (methyl) acrylate can be used more than a kind.The number of aromatic ring is for example 1,2 or 3, is preferably 1.
((C) composition: the compound with 1 sulfydryl)
The compound containing sulfydryl in present embodiment can list following material.
((C1) composition: alkanethiol)
Alkanethiol is the mercaptan with alkyl.Alkyl can be that linear chain structure can be also branched structure.Among alkanethiol, the alkanethiol shown in preferred following formula (1).
C
nh
2n+1sH formula (1)
(n is integer)
N is preferably 4～19, and more preferably 6～12.
Preferred decane mercaptan and/or dodecyl mercaptans among alkanethiol.
((C2) composition: carboxyl mercaptan)
Carboxyl mercaptan is the mercaptan with carboxyl.Among carboxyl mercaptan, the carboxyl mercaptan shown in preferred following formula (2).
ROOC(CH
2)
psH formula (2)
(R is the alkyl of hydrogen or carbon number 1～19, and p is integer)
The carbon number of the alkyl of above-mentioned R is preferably 2～16, and more preferably 5～12.
Above-mentioned p is preferably 1～30, and more preferably 1～2.
As carboxyl mercaptan, can list: Thiovanic acid, β-mercaptopropionic acid, mercaptoacetate (Methyl Thioglycolate, Thiovanic acid monooctyl ester etc.), β-mercaptopropionic acid ester (3-mercapto-propionate, 3-mercapto-propionate, 3-thiohydracrylic acid n-octyl, 3-thiohydracrylic acid stearyl ester) etc.In carboxyl mercaptan, preferred Thiovanic acid and/or β-mercaptopropionic acid.
((D) composition: Photoepolymerizationinitiater initiater)
As the Photoepolymerizationinitiater initiater of present embodiment, can list following material.As Photoepolymerizationinitiater initiater, so long as make homopolymer glass transition temperature, be that the material that the polymerization of (methyl) acrylate of-100～60 ℃ starts just has no particular limits.
As Photoepolymerizationinitiater initiater, can list ultraviolet polymerization initiator, visible ray polymerization starter etc., any one can use ad lib.As ultraviolet polymerization initiator, can list: bitter almond oil camphor system, benzophenone series, methyl phenyl ketone system etc.As visible ray polymerization starter, can list acylphosphine oxide system, thioxanthone system, metallocene system, quinone system, alpha-aminoalkyl methyl phenyl ketone system etc.
As Photoepolymerizationinitiater initiater, can list benzophenone, 4-phenyl benzophenone, benzoyl phenylformic acid, 2,2-diethoxy acetophenone, two diethylin benzophenone, benzil, bitter almond oil camphor, benzoyl isopropyl ether, benzil dimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone, 1-(4-isopropyl phenyl) 2-hydroxy-2-methyl propane-1-ketone, 1-(4-(2-hydroxyl-oxethyl)-phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, camphorquinone, TMDPO, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholine propane-1-ketone, 2-benzil-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone-1, 2-dimethylamino-2-(4-methyl-benzil)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, two (2,6-dimethoxy benzoyls)-2,4,4-trimethylammonium-amyl group phosphine oxide etc.
((E) composition: (A) and (B) (methyl) acrylate in addition)
The curable resin composition of present embodiment, especially for the object that makes the cementability of each adherend further improve, as (E) composition, can contain except (A) polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy system (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate, and the oligopolymer of skeleton with the hydrogenation thing of diene polymerization system (methyl) acrylate, (B) homopolymer glass transition temperature is (methyl) acrylate beyond (methyl) acrylate of-100～60 ℃.
As this (E) composition ((A) and (B) (methyl) acrylate in addition), can use variedly simple function (methyl) acrylate, 2 officials can, 3 officials can, 4 officials can, 5 officials can, 6 officials multifunctional (methyl) acrylate that can wait etc.Among these, preferably simple function (methyl) acrylate or 2 officials can (methyl) acrylate.
In (E) composition of present embodiment, as simple function (methyl) acrylate, can list: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) stearyl acrylate ester, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, (methyl) cyclohexyl acrylate, two cyclopentyl (methyl) acrylate (dicyclopentanyl methacrylate), (methyl) isobornyl acrylate, (methyl) vinylformic acid benzyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid phenoxy group TEG ester, (methyl) vinylformic acid phenoxy group macrogol ester, (methyl) vinylformic acid Nonylphenoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy TEG ester, (methyl) vinylformic acid methoxyl group binaryglycol ester, (methyl) vinylformic acid oxyethyl group binaryglycol ester, (methyl) vinylformic acid butoxyethyl, (methyl) vinylformic acid butoxytriglycol ester, (methyl) acrylic acid-2-ethyl hexyl macrogol ester, (methyl) vinylformic acid nonyl phenyl polypropylene glycol ester, (methyl) vinylformic acid methoxyl group dipropylene glycol ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid glyceryl ester, (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, epoxy chloropropane (being slightly designated as below ECH) modification (methyl) butyl acrylate, epoxy chloropropane (being slightly designated as below ECH) modification phenoxy group (methyl) acrylate, oxyethane (being slightly designated as below EO) modification phthalic acid (methyl) acrylate, EO modification succsinic acid (methyl) acrylate, caprolactone modification (methyl) vinylformic acid 2-hydroxy methacrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, morpholine (methyl) acrylate, EO modified phosphate (methyl) acrylate etc.Also can list such (methyl) acrylate with imide of imide (methyl) acrylate (goods name: M-140, East Asia Synesis Company manufacture) etc.
Among above-mentioned (E) composition, as simple function (methyl) acrylate, object for improving with cementability with the polyolefine headed by cyclic olefin polymer etc., can list: (methyl) acrylate with dicyclopentenyl headed by dicyclopentenyl oxygen base ethyl (methyl) acrylate, dicyclopentenyl oxygen base propyl group (methyl) acrylate, dicyclopentenyl (methyl) acrylate etc. etc.
(E), among the simple function in composition (methyl) acrylate, from improving the viewpoint with the cementability of cycloolefin, more preferably there is (methyl) acrylate and/or (methyl) isobornyl acrylate of dicyclopentenyl.
Among (E) composition of present embodiment, as multifunctional (methyl) acrylate, can list: two (methyl) propylene acidylate isocyanuric acid ester, three (methyl) propylene acidylate isocyanuric acid ester, 1,3-dibutylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, EO(oxyethane) modified bisphenol A two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, ECH(epoxy chloropropane) modification hexahydrophthalic acid two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, EO modification neopentyl glycol two (methyl) acrylate, caprolactone modification hydroxypivalic acid ester neopentyl glycol two (methyl) acrylate, stearic acid modified tetramethylolmethane two (methyl) acrylate, ECH modification diallyphthalate acid esters, poly-(ethylene glycol-tetramethylene glycol) two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ECH modification propylene glycol two (methyl) acrylate, tristane dimethanol (methyl) acrylate, tripropylene glycol two (methyl) acrylate, triglycerin two (methyl) acrylate, ECH modified glycerol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, EO modified phosphate three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate, PO modification trimethylolpropane tris (methyl) acrylate, three ((methyl) acryloxy ethyl) isocyanuric acid ester, Dipentaerythritol six (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane oxyethyl group four (methyl) acrylate.
Among above-mentioned (E) composition, as multifunctional (methyl) acrylate, also can list: with (methyl) acrylate with dicyclopentenyl headed by dicyclopentenyl two (methyl) acrylate etc. etc.
Among multifunctional (methyl) acrylate in above-mentioned (E) composition, from the deliquescent viewpoint of oligopolymer, more preferably trimethylolpropane tris (methyl) acrylate and/or tristane dimethanol (methyl) acrylate.
In present embodiment, the object for raising with the closing force of glass, can contain silane coupling agent.
Curable resin composition for present embodiment, as essential component, contain: (A) select free polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy system (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate, and a kind of above (methyl) origoester acrylate in the group that forms of the oligopolymer of skeleton with the hydrogenation thing of diene polymerization system (methyl) acrylate, (B) homopolymer glass transition temperature is (methyl) acrylate of-100～60 ℃, (C) there is the compound of 1 sulfydryl, (D) Photoepolymerizationinitiater initiater.The curable resin composition of present embodiment can carry out solidifying by ultraviolet ray or visible ray.
From the viewpoint that cementability uprises, solidified nature improves, in the curable resin composition of present embodiment, at (A) composition with (B) in total 100 mass parts of composition, (A) composition is preferably (A) composition with (B) mass ratio of composition: (B) composition=10～95:90～5, more preferably (A) composition: (B) composition=25～90:75～10.There is no particular limitation for the numerical value of (A) composition when representing this ratio, for example, can be 5,10,20,30,40,50,60,70,80,90 or 95, also can the scope in arbitrary value wherein in.In addition, there is no particular limitation for the numerical value of (B) composition when representing this ratio, for example, can be 5,10,20,30,40,50,60,70,80,90 or 95, also can the scope in arbitrary value wherein in.
For the usage quantity of (C) composition, total 100 mass parts with respect to (A) composition, (B) composition and (E) composition of using as required, are preferably 0.01～10 mass parts, more preferably 0.1～8 mass parts.To this usage quantity, there is no particular limitation, for example, can be 0.01,0.05,0.1,0.5,1,2,3,4,5,6,7,8,9,10 or 15, also can the scope in arbitrary value wherein in.
For the usage quantity of (D) composition, total 100 mass parts with respect to (A) composition, (B) composition and (E) composition of using as required, are preferably 0.1～20 mass parts, more preferably 0.2～10 mass parts.To this usage quantity, there is no particular limitation, for example, can be 0.01,0.05,0.1,0.5,1,2,3,4,5,6,7,8,9,10,15,20 or 25, also can the scope in arbitrary value wherein in.
For the usage quantity of (E) composition, with respect to (A) composition and (B) total 100 mass parts of composition, be preferably 1～30 mass parts, more preferably 5～15 mass parts.To this usage quantity, there is no particular limitation, for example, can be 0.1,1,2,3,4,5,6,7,8,9,10,15,20,30 or 35, also can the scope in arbitrary value wherein in.
And then, in order to make the curing change of part of ingress of air of curable resin composition of present embodiment rapid, can use various paraffin class.
And then, for the object that maintains storage stability, can use commercially available oxidation inhibitor that comprises stopper etc.
It should be noted that, in addition, according to expectation, also can use the known materials such as elastomerics, softening agent, weighting agent, tinting material or rust-preventive agent.
Curable resin composition in present embodiment can be used as adhesive composite.In addition, in an embodiment, thereby can adherend be engaged or be covered by the cured body of adhesive composite making complex body.Cured body can obtain by for example adhesive composite being carried out to UV irradiation.Various materials for adherend, be preferably in the group that polyolefine such as selecting free cellulosetri-acetate, fluorine based polymer, polyester, polycarbonate, cyclic olefin polymer, glass, metal form more than a kind, more preferably select in the group that free polycarbonate, polyolefine, glass forms more than a kind.
With the adherend that the curable resin composition of present embodiment is bonding, can after solidifying completely, reprocess (recycling).Method as reprocessing, has no particular limits, can be by making adherend separated from one another to the loading of load 0.01～100N between the adherend of fitted a kind or 2 kinds, and the adherend after recycling separation.
Above embodiments of the present invention are narrated, but foregoing is illustration of the present invention, also can adopts above-mentioned various formations in addition.In addition, also can combine and adopt the formation of recording in above-mentioned embodiment.
Embodiment
The present invention will be described in more detail below to enumerate experimental example, but the present invention is not limited thereto.It should be noted that the following compound that respectively become component selections in the curable resin composition of recording in embodiment.
As selecting free polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy system's (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate and thering is a kind of above (methyl) origoester acrylate (A) in the group that the oligopolymer of skeleton of the hydrogenation thing of diene polymerization system (methyl) acrylate forms
(A-1) 1,2-polybutadiene-modified polyurethane series methacrylate oligomers (" TE-2000 " that Japanese Cao Da company manufactures) (number-average molecular weight 2000,2 officials of the polystyrene conversion obtaining by GPC can methacrylate oligomers)
(A-2) mixture of acrylic ester polymer and polyurethane series origoester acrylate (" PM-654 " that Osaka organic chemistry industrial manufactures) (origoester acrylates of number-average molecular weight 20000,2 officials' energy of the polystyrene conversion obtaining by GPC)
(A-3) polyester-polyurethane is origoester acrylate (" KHP-17 " that Gen Shang industrial manufactures) (origoester acrylates of weight-average molecular weight 40000,2 officials' energy of the polystyrene conversion obtaining by GPC)
(A-4) dibutylene glycol polyurethane series origoester acrylate (" UV-3000B " that Japanese synthetic chemistry company manufactures) (weight-average molecular weight 18000,2 officials of the polystyrene conversion obtaining by GPC can origoester acrylates)
(A-5) polycarbonate polyurethane is origoester acrylate (" UN-9000PEP " that Gen Shang industrial manufactures) (origoester acrylates of weight-average molecular weight 5000,2 officials' energy of the polystyrene conversion obtaining by GPC)
(A-6) polyether-polyurethane is origoester acrylate (" UV-3700B " that Japanese synthetic chemistry company manufactures) (weight-average molecular weight 38000,2 officials of the polystyrene conversion obtaining by GPC can origoester acrylates)
As homopolymer glass transition temperature, be (methyl) acrylate (B) of-100～60 ℃,
(B-1) EO modified acroleic acid nonyl phenyl ester (" M-111 " that East Asia Synesis Company manufactures: homopolymer glass transition temperature :-25 ℃)
(B-2) the different stearyl ester of vinylformic acid (" ISTA " that Osaka organic chemistry industrial manufactures: homopolymer glass transition temperature :-18 ℃)
(B-3) (Japan changes into " 4-HBA " that company manufactures to vinylformic acid-4-hydroxyl butyl ester: homopolymer glass transition temperature :-80 ℃)
As the compound (C) containing sulfydryl,
(C-1) n-decane mercaptan (" decane mercaptan " that Aldrich company manufactures)
(C-2) n-dodecane mercaptan (" dodecyl mercaptans " that Aldrich company manufactures)
(C-3) β-mercaptopropionic acid (" BMPA " that SC organic chemistry industrial manufactures)
(C-4) 3-thiohydracrylic acid n-octyl (" NOMP " that SC organic chemistry industrial manufactures)
As Photoepolymerizationinitiater initiater (D),
(D-1) 1-hydroxy-cyclohexyl phenyl ketone (" Irgacure184 " that CIBA SPECIALTY CHEMICALS manufactures)
(D-2) two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide (" Irgacure819 " that CIBA SPECIALTY CHEMICALS manufactures)
As (A) and (B) (methyl) acrylate (E) in addition,
(E-1) (Hitachi changes into " FA-511AS " that company manufactures to dicyclopentenyl acrylate: homopolymer glass transition temperature: 120 ℃)
(E-2) dicyclopentenyl diacrylate (" DCP " that Xin Zhong village chemical company manufactures: homopolymer glass transition temperature: 100 ℃)
(E-3) tristane dimethanol acrylate (" KAYARADR-684 " that Japanese chemical drug company manufactures: homopolymer glass transition temperature: 150 ℃)
(E-4) Viscoat 295 (" A-TMPT " that Xin Zhong village chemical industrial company manufactures: homopolymer glass transition temperature: >250 ℃)
(E-5) (Hitachi changes into " IBXA " that industrial manufactures to isobornyl acrylate: homopolymer glass transition temperature: 180 ℃)
As a comparative example,
(C-5) DMDO: triethylene glycol two mercaptan (" DMDO " that Wan Shan oiling company manufactures)
(C-6) 3-sulfydryl propyl trimethoxy silicane (" KBM-803 " that chemical industrial company of SHIN-ETSU HANTOTAI manufactures)
Various physical property are measured as follows.
(second-order transition temperature) measured according to Measurement of Dynamic Viscoelasticity.
(light solidified) measured at 23 ℃ of temperature.About light solidified, the curable resin composition that is 0.1mm at the surface coated thickness of TEMPAX glass (25 * 25 * 2mm).Thereafter, the solidification equipment of manufacturing with the Fusion company that has used electrodeless discharge lamp, at accumulated light 2000mJ/cm
2condition under the UV light of illumination wavelength 365nm, it is solidified.It should be noted that, the evaluation of light solidified is calculated by FT-IR.Using the ownership peak that has neither part nor lot in reaction as reference peaks, after pre-irradiation, confirm 1600cm
-1deng the decay at the two keys ownership of C=C peak, and calculate.
(evaluation of polyethylene terephthalate (PET) cementability (peeling off bonding strength) between polyethylene terephthalate test film) is by biaxial stretch-formed PET film (LUMIRROR T60, mean thickness 190 μ m, TORAY INDUSTRIES, INC. test film (50mm * 10mm * 0.19mm) manufacture) is bonded to each other, wherein, use curable resin composition as adhesive composite, the thickness of adhesive linkage is that 30 μ m and bond area are long 40mm * wide 10mm.After solidifying by rayed, by the 2 film ends, place to by this bonding test film of caking agent, not closely sealed, stretch, thereby stripping film closely sealed part is each other measured initial 180 ° and is peeled off bonding strength.The method that rayed condition is recorded according to (light solidified).It should be noted that, peel off bonding strength (unit: N/cm) for using extensometer, the mensuration to carry out for draw speed 10mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(glass cementation is evaluated (the stretching bonding strength between thermal glass test film)) is bonded to each other thermal glass test film (25mm * 25mm * 2.0mm), wherein, Teflon (registered trademark) band of used thickness 80 μ m * width 12.5mm * length 25mm is as spacer (spacer), with bonding (the bond area 3.125cm of curable resin composition
2).The method that rayed condition is recorded according to (light solidified).After making under these conditions adhesive composite solidify, the adhesive composite " G-55 " that further uses Denki Kagaku Kogyo kabushiki to manufacture, the bonding steel plate galvanized in the two sides of test film (100mm * 25mm * 2.0mm, ENGINEERING TEST SERVICE company manufacture).After solidifying, use by this bonding test film of adhesive composite, steel plate galvanized is clamped, measure initial tensile shear bonding strength.Tensile shear bonding strength (unit: MPa) for using extensometer mensuration to carry out for draw speed 10mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(evaluation of cyclic olefin polymer (COP) cementability (peeling off bonding strength) between cyclic olefin polymer test film) is bonded to each other the test film (50mm * 10mm * 0.04mm) of COP film (ZEONOR, mean thickness 40 μ m, ZEON CORPORATION manufacture), wherein, use curable resin composition as adhesive composite, the thickness of adhesive linkage is that 10 μ m and bond area are long 40mm * wide 10mm.After solidifying by rayed, by the 2 film ends, place to by this bonding test film of adhesive composite, not closely sealed, stretch, thereby stripping film closely sealed part is each other measured initial 180 ° and is peeled off bonding strength.The method that rayed condition is recorded according to (light solidified).It should be noted that, peel off bonding strength (unit: be N/cm) to use extensometer, the mensuration to carry out for draw speed 10mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(cellulosetri-acetate cementability is evaluated (peeling off bonding strength) between cellulosetri-acetate test film) is bonded to each other the test film (width 50mm * length 10mm * thickness 0.04mm) of cellulosetri-acetate (TAC) film (mean thickness 40 μ m, FUJIFILM CORPORATION company manufacture), wherein, use curable resin composition as adhesive composite, the thickness of adhesive linkage is that 10 μ m and bond area are long 40mm * wide 10mm.After solidifying by rayed, by the 2 film ends, place to by this bonding test film of adhesive composite, not closely sealed, stretch, thereby stripping film closely sealed part is each other measured initial 180 ° and is peeled off bonding strength.The method that rayed condition is recorded according to (light solidified).Peel off bonding strength (unit: be N/cm) to use extensometer, the mensuration to carry out for draw speed 50mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(fluorine based polymer cementability is evaluated (peeling off bonding strength) between fluorine film test film) is bonded to each other the test film (width 50mm * length 10mm * thickness 0.04mm) of PVDF film (" DX film " that mean thickness 40 μ m, Denki Kagaku Kogyo kabushiki manufacture), wherein, use curable resin composition as adhesive composite, the thickness of adhesive linkage is that 10 μ m and bond area are long 40mm * wide 10mm.After solidifying by rayed, by the 2 film ends, place to by this bonding test film of adhesive composite, not closely sealed, stretch, thereby stripping film closely sealed part is each other measured initial 180 ° and is peeled off bonding strength.The method that rayed condition is recorded according to (light solidified).Peel off bonding strength (unit: be N/cm) to use extensometer, the mensuration to carry out for draw speed 50mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(polycarbonate cementability is evaluated (the stretching bonding strength between polycarbonate test film)) is bonded to each other polycarbonate (" PANLITE " that Di Ren company manufactures) test film (width 25mm * length 25mm * thickness 2.0mm), wherein, Teflon (registered trademark) band of used thickness 80 μ m * width 11.5mm * length 25mm, as spacer, carrys out bonding (bond area 3.125cm with curable resin composition as adhesive composite
2).The method that rayed condition is recorded according to (light solidified).After making under these conditions adhesive composite solidify, the adhesive composite " G-55 " that further uses Denki Kagaku Kogyo kabushiki to manufacture, bonding steel plate galvanized on the two sides of test film (100mm * 25mm * 2.0mm, ENGINEERING TEST SERVICE company manufacture).After solidifying, use by this bonding test film of adhesive composite, steel plate galvanized is clamped, measure initial tensile shear bonding strength.Tensile shear bonding strength (unit: be MPa) to use extensometer mensuration to carry out for draw speed 10mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(metal sticking is evaluated (the stretching bonding strength between SPCC test film)) is bonding by SPCC test film (width 25mm * length 25mm * thickness 1.6mm) and TEMPAX glass (width 25mm * length 25mm * thickness 2mm), wherein, Teflon (registered trademark) band of used thickness 80 μ m * width 11.5mm * length 25mm, as spacer, carrys out bonding (bond area 3.125cm with curable resin composition as adhesive composite
2).The method that rayed condition is recorded according to (light solidified).After making under these conditions adhesive composite solidify, further use the adhesive composite " G-55 " of Denki Kagaku Kogyo kabushiki's manufacture TEMPAX test film side bonds steel plate galvanized (width 100mm * length 25mm * thickness 2.0mm, ENGINEERING TEST SERVICE company manufacture).After solidifying, use by this bonding test film of adhesive composite, steel plate galvanized is clamped, measure initial tensile shear bonding strength.Tensile shear bonding strength (unit: be MPa) to use extensometer mensuration to carry out for draw speed 10mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(humidity resistance evaluation (the stretching bonding strength between the thermal glass test film after hot and humid exposure)) used curable resin composition as adhesive composite, TEMPAX glass (25mm * 25mm * 2mm) is bonded to each other and is solidified, wherein, the thickness of adhesive linkage is that 100 μ m and bond area are 1.0mm
2.The method that rayed condition is recorded according to (light solidified).After solidifying, use constant temperature and humidity cabinet, will by bonding this test film of adhesive composite, be exposed to lower 1000 hours of the environment of 85 ℃ of temperature, relative humidity 85%.Use the test film after exposing to measure tensile shear bonding strength.Whether the outward appearance at the bonding position of visual observation, check xanthochromia.After exposure, further use the adhesive composite " G-55 " of Denki Kagaku Kogyo kabushiki's manufacture TEMPAX test film side bonds steel plate galvanized (width 100mm * length 25mm * thickness 2.0mm, ENGINEERING TEST SERVICE company manufacture).After solidifying, use by this bonding test film of adhesive composite, steel plate galvanized is clamped, measure initial tensile shear bonding strength.Tensile shear bonding strength (unit: be MPa) to use extensometer mensuration to carry out for draw speed 10mm/ minute under the environment of 23 ℃ of temperature, humidity 50%.
(outward appearance is observed (xanthochromia index)) used curable resin composition as adhesive composite, TEMPAX glass (25mm * 25mm * 2mm) is bonded to each other and is solidified, and wherein, the thickness of adhesive linkage is that 100 μ m and bond area are 1.0mm
2.The method that rayed condition is recorded according to (light solidified).After solidifying, using the Δ b value to by this bonding colour assessment apparatus (" UV-VISIBLE SPECTROPOHOTOMETER " that SHIMADZU company manufactures) mensuration for test film of adhesive composite as xanthochromia index.
(experimental example)
The curable resin composition forming shown in preparation table 1～4, measures various physical property.The results are shown in table 1～4.
[table 1]
[table 2]
[table 3]
[table 4]
According to this experimental example, know following item.Cementability of the present invention is large.The present invention has the flexibility of the degree of the distortion that can follow adherend under the environment of heating, so humidity resistance is large.When being used as the DMDO with more than 2 compound of sulfydryl, flexibility, cementability are little.
utilizability in industry
So the present invention can give sufficient cementability owing to being difficult to sneak into bubble, can fit transparency carrier or laminating are printed part.The present invention is because humidity resistance is large, so can use under the environment of heating.The present invention's utilizability is industrially large.
Claims (16)
1. a curable resin composition, it contains:
(A) select free polyurethane series (methyl) origoester acrylate, polyester system (methyl) origoester acrylate, polyethers system (methyl) origoester acrylate, epoxy system's (methyl) origoester acrylate, diene polymerization system (methyl) origoester acrylate and there is a kind of above (methyl) origoester acrylate in the group that the oligopolymer of skeleton of the hydrogenation thing of diene polymerization system (methyl) acrylate forms
(B) homopolymer glass transition temperature is (methyl) acrylate of-100～60 ℃,
(C) select the compound in a kind of above molecule in the group that free alkanethiol and carboxyl mercaptan forms with 1 sulfydryl, and
(D) Photoepolymerizationinitiater initiater.
2. curable resin composition according to claim 1, wherein, its also contain described (A) and (B) (methyl) acrylate in addition as (E) composition.
3. curable resin composition according to claim 2, wherein, described (E) composition is trimethylolpropane tris (methyl) acrylate and/or tristane dimethanol (methyl) acrylate.
4. according to the curable resin composition described in claim 1～3 wantonly 1, wherein, the compound that the molecule of described (C) contains 1 sulfydryl is the alkanethiol shown in following formula (1),
C
nh
2n+1sH formula (1)
In formula (1), the integer that n is 4～19.
5. according to the curable resin composition described in claim 1～3 wantonly 1, wherein, the compound that the molecule of described (C) contains 1 sulfydryl is the carboxyl mercaptan shown in following formula (2),
ROOC(CH
2)
psH formula (2)
In formula (2), R is the alkyl of hydrogen or carbon number 1～19, and p is integer.
6. according to the curable resin composition described in claim 1～5 wantonly 1, wherein, the weight-average molecular weight of described (A) composition is 500～100000.
7. according to the curable resin composition described in claim 1～5 wantonly 1, wherein, the number-average molecular weight of described (A) composition is 500～100000.
8. according to the curable resin composition described in claim 1～7 wantonly 1, wherein, described (A) composition is polyurethane series (methyl) origoester acrylate.
9. an adhesive composite, it comprises the curable resin composition described in wantonly 1 in claim 1～8.
10. a cured body, its cured body that is adhesive composite claimed in claim 9.
11. 1 species complexs, it is by cured body claimed in claim 10, adherend to be covered or engaged to form.
12. complex bodys according to claim 11, wherein, described adherend be select in the group that free cellulosetri-acetate, fluorine based polymer, polyester, polycarbonate, polyolefine, glass and metal form more than a kind.
13. 1 kinds of touch panel duplexers, it is by adhesive composite claimed in claim 9, adherend laminating to be formed.
14. 1 kinds of liquid crystal panel duplexers, it is by adhesive composite claimed in claim 9, adherend laminating to be formed.
15. 1 kinds of indicating meters, it has used the touch panel duplexer described in claim 13.
16. 1 kinds of indicating meters, it has used the liquid crystal panel duplexer described in claim 14.
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| JP2011-185049 | 2011-08-26 | ||
| JP2011185049 | 2011-08-26 | ||
| PCT/JP2012/071425 WO2013031678A1 (en) | 2011-08-26 | 2012-08-24 | Curable resin composition |
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| KR (1) | KR101942546B1 (en) |
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| CN114787213A (en) * | 2019-12-13 | 2022-07-22 | 日东新兴有限公司 | Curable composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20140051929A (en) | 2014-05-02 |
| WO2013031678A1 (en) | 2013-03-07 |
| JP6035241B2 (en) | 2016-11-30 |
| TW201317315A (en) | 2013-05-01 |
| JPWO2013031678A1 (en) | 2015-03-23 |
| KR101942546B1 (en) | 2019-01-25 |
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