CN105339348B - (methyl) acrylate derivative of Sulfide-containing Hindered and the adhesion improver containing the derivative - Google Patents
(methyl) acrylate derivative of Sulfide-containing Hindered and the adhesion improver containing the derivative Download PDFInfo
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- CN105339348B CN105339348B CN201580000173.6A CN201580000173A CN105339348B CN 105339348 B CN105339348 B CN 105339348B CN 201580000173 A CN201580000173 A CN 201580000173A CN 105339348 B CN105339348 B CN 105339348B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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Abstract
The present invention provides a kind of (methyl) acrylate derivative of the excellent Sulfide-containing Hindered of adhesion improvement.(methyl) acrylate derivative of the Sulfide-containing Hindered of the present invention has the structure shown in following formula 1.(a in formula is 1~3 integer, the integer that b be 0 or 1, c be 1~3, a and b and c's and be 4.R1For methylene, ethylidene or isopropylidene.R2For the functional group of the divalent shown in following formula 2 or following formula 3.R3For methyl or ethyl.R4For the alkyl of carbon number 1~12.)(R5For hydrogen atom or methyl.)(R5For hydrogen atom or methyl.)
Description
Technical field
The present invention relates to a kind of (methyl) acrylate derivative of new Sulfide-containing Hindered suitable for adhesion improver etc.
Thing.
Background technology
In the past, to when being coated with various coating on the inorganic substrates such as glass, in order to improve adhesion, silane is added into coating
The adhesion such as coupling agent improver (for example, referring to patent document 1).But following problem occurs, if because heating silane is even
Join agent then its decomposition, if using on a production line, the reason for separating out silica in the heating furnaces such as baking oven and form pollution.This
Outside, for independent silane coupler, it cannot be said that its adhesion improvement is abundant, such as in most cases, by same
The adhesion auxiliary agent such as amine, phosphate, polyurethane resin of the salt or imidazoles of Shi Tianjia titaniums, zirconium etc. etc., can realize practical water
Accurate adhesion.In addition, the addition of adhesion auxiliary agent is directed not only to the increase of manufacturing process and cost, also exist due to addition patch
Attached property auxiliary agent and cause coating storage stability at room temperature to deteriorate, the problem of heat resistance, the hardness of film are reduced.
Patent Document 2 discloses in order to solve the above problems, by by the urea derivative of the Sulfide-containing Hindered of specific structure
Used as adhesion improver, even if without adhesion auxiliary agent, can also improve adhesion.
In addition, Patent Document 3 discloses contain the addition poly-thiol compound in silane coupler or polyenoid chemical combination
The addition reaction of thing and the Photocurable resin composition of Photoepolymerizationinitiater initiater, it has given play to excellent bonding force.
Prior art literature
Patent document
Patent document 1：Unexamined Patent 7-300491 publications
Patent document 2：JP 2013-249282 publications
Patent document 3：JP 2001-89568 publications
The content of the invention
The technical problem to be solved in the present invention
However, in cold district, the adhesion to coating relative to the film base material with flexibility is studied, it is tied
Fruit understands there are following problems：By the urea derivative or poly-thiol compound or polyenic compounds and silicon of the Sulfide-containing Hindered
The addition reaction of alkane coupling agent is as the adhesion improver of coating in the case of use, and resulting film lacks soft
Property, film is also easy to produce crackle when bending.
The present invention be in view of above-mentioned actual state and complete, its object is to provide a kind of material, the material addition
When coating etc., in the case that cold district is without adhesion auxiliary agent, the high adhesion relative to base material can be also played
Improvement, and resulting film has flexibility.
Solve the technological means of technical problem
To achieve these goals, (methyl) acrylate derivative of Sulfide-containing Hindered of the invention has shown in following formula 1
Structure.
[chemical formula 1]
(a in formula is 1~3 integer, the integer that b be 0 or 1, c be 1~3, a and b and c's and be 4.R1For methylene,
Ethylidene or isopropylidene.R2For the divalent functional group shown in following formula 2 or following formula 3.R3For methyl or ethyl.R4For carbon atom
The alkyl of number 1~12.)
[chemical formula 2]
(R5For hydrogen atom or methyl.)
[chemical formula 3]
(R5For hydrogen atom or methyl.)
(methyl) acrylate derivative with the Sulfide-containing Hindered of structure shown in above-mentioned formula 1, preferably as shown in following formula 4
Acyclic compound is formed with the multi-thiol compound reaction shown in following formula 5.
[chemical formula 4]
(the R in formula4For the alkyl of carbon number 1~12.R7For hydrogen atom or methyl.)
[chemical formula 5]
(g in formula is 0 or 1, h are 3 or 4, g and h's and be 4.R1For methylene, ethylidene or isopropylidene.R3For first
Base or ethyl.)
In addition, (methyl) acrylate derivative of the Sulfide-containing Hindered of the present invention can also be containing the structure shown in following formula 6.
[chemical formula 6]
(d in formula is 1~5 integer, and e is 0~2 integer, and f is 1~5 integer, d and e and f's and be 6.R1For
Methylene, ethylidene or isopropylidene.R2For the divalent functional group shown in following formula 2 or following formula 3.R3For methyl or ethyl.R4
For the alkyl of carbon number 1~12.R6For 6 valency functional groups shown in following formula 7.)
[chemical formula 7]
(R5For hydrogen atom or methyl.)
[chemical formula 8]
(R5For hydrogen atom or methyl.)
[chemical formula 9]
(methyl) acrylate derivative of the Sulfide-containing Hindered of the structure with shown in formula 6 is preferably as shown in following formula 4
Acyclic compound with shown in following formula 8 multi-thiol compound reaction form.
[chemical formula 10]
(the R in formula4For the alkyl of carbon number 1~12.R7For hydrogen atom or methyl.)
[chemical formula 11]
(i in formula is 0~2 integer, and j is 4~6 integer, i and j's and be 6.R1For methylene, ethylidene or different
Propylidene.R3For methyl or ethyl.R6For 6 valency functional groups shown in following formula 7.)
[chemical formula 12]
In addition, the present invention also provides a kind of adhesion improver, it is derived with (methyl) acrylate of the Sulfide-containing Hindered
Any one of thing is active ingredient.
In addition, in this manual, " (methyl) acrylate " refers to include " methacrylate " and " acrylate "
Both concepts.In addition, the record on " 0 0~×× " in this specification, as long as no other records, be " 00 with
Below upper, ×× " meaning.
Invention effect
In the case where (methyl) acrylate derivative of the Sulfide-containing Hindered of the present invention is added in coating etc., for example, it is
Make under -10 DEG C of cold environment, it may have given play to high adhesion relative to base material in the case of without adhesion auxiliary agent and changed
Kind effect, and resulting film has the effect of flexibility.It is believed that the effect above is because in cold environments, having
The ester group of specific carbochain assigns coating flexibility, and the ester group does not hinder the close of thioether group and base material, therefore effectively plays
The adhesion improvement that thioether group is produced.
Brief description of the drawings
Fig. 1 is the IR spectrum of the synthetic 1 obtained in embodiment 1-1；
Fig. 2 is the IR spectrum of the synthetic 2 obtained in embodiment 1-2；
Fig. 3 is the IR spectrum of the synthetic 3 obtained in embodiment 1-3；
Fig. 4 is the IR spectrum of the synthetic 4 obtained in embodiment 1-4；
Fig. 5 is the IR spectrum of the synthetic 5 obtained in embodiment 1-5；
Fig. 6 is the IR spectrum of the synthetic 6 obtained in embodiment 1-6；
Fig. 7 is the synthetic 1 obtained in embodiment 1-11H-NMR is composed；
Fig. 8 is the synthetic 2 obtained in embodiment 1-21H-NMR is composed；
Fig. 9 is the synthetic 3 obtained in embodiment 1-31H-NMR is composed；
Figure 10 is the synthetic 4 obtained in embodiment 1-41H-NMR is composed；
Figure 11 is the synthetic 5 obtained in embodiment 1-51H-NMR is composed；
Figure 12 is the synthetic 6 obtained in embodiment 1-61H-NMR is composed.
Embodiment
Hereinafter, to the embodiment that the present invention embodies is described in detail.
(methyl) the acrylate derivative ＞ of ＜ Sulfide-containing Hindereds
(embodiment 1)
(methyl) acrylate derivative of the Sulfide-containing Hindered of present embodiment is the compound shown in following formula 1.
[chemical formula 13]
(a in formula is 1~3 integer, the integer that b be 0 or 1, c be 1~3, a and b and c's and be 4.R1For methylene
Base, ethylidene or isopropylidene.R2For the divalent functional group shown in following formula 2 or following formula 3.R3For methyl or ethyl.R4For carbon
The alkyl of atomicity 1~12.)
[chemical formula 14]
(R5For hydrogen atom or methyl.)
[chemical formula 15]
(R5For hydrogen atom or methyl.)
It is used as the R in the formula 14Carbon number 1~12 alkyl, straight chained alkyl, the alkane with side chain can be included
Base, cyclic alkyl.R in the formula 11It is special from adhesion improvement is improved for methylene, ethylidene, isopropylidene
Not preferred ethylidene, isopropylidene.
In the case where (methyl) acrylate derivative of the Sulfide-containing Hindered shown in the formula 1 is added in coating etc.,
For example in the environment of -10 DEG C, it may have following excellent effects：Sent out in the case of without adhesion auxiliary agent relative to base material
Shoot high adhesion improvement and give resulting soft film coating.Further, (the first of the Sulfide-containing Hindered shown in the formula 1
Base) acrylate derivative is smaller than the molecular weight of (methyl) acrylate derivative of the Sulfide-containing Hindered of embodiment 2 described later, because
And dissolubility is excellent.Therefore, for most resin, (methyl) acrylate derivative of the Sulfide-containing Hindered shown in the formula 1 has
The intermiscibility higher than (methyl) acrylate derivative of the Sulfide-containing Hindered of embodiment 2, therefore extensive coating can be used, lead to
It is high with property.
(embodiment 2)
As the embodiment 2 of (methyl) acrylate derivative of Sulfide-containing Hindered, the change shown in following formula 6 can be included
Compound.
[chemical formula 16]
(d in formula is 1~5 integer, and e is 0~2 integer, and f is 1~5 integer, d and e and f's and be 6.R1For
Methylene, ethylidene or isopropylidene.R2For the divalent functional group shown in following formula 2 or following formula 3.R3For methyl or ethyl.R4
For the alkyl of carbon number 1~12.R6For 6 valency functional groups shown in following formula 7.)
[chemical formula 17]
(R5For hydrogen atom or methyl.)
[chemical formula 18]
(R5For hydrogen atom or methyl.)
[chemical formula 19]
It is used as the R in the formula 64Carbon number be 1~12 alkyl, straight chained alkyl can be included, with side chain
Alkyl, cyclic alkyl.R in the formula 61For methylene, ethylidene, isopropylidene, from improving adhesion improvement,
Particularly preferably ethylidene, isopropylidene.
For (methyl) acrylate derivative of the Sulfide-containing Hindered shown in the formula 6, such as even in -10 DEG C of cold ring
Under border, as long as being made an addition on a small quantity as adhesion improver in the resin combination of coating or bonding agent etc., it becomes possible to assign it
High adhesion, and assign obtained by film with flexibility.
The manufacture method ＞ of (methyl) acrylate derivative of ＜ Sulfide-containing Hindereds
, for example can be by making for (methyl) acrylate derivative of the Sulfide-containing Hindered of the embodiment 1 shown in the formula 1
Having shown in (methyl) acrylate-based acyclic compound (hereinafter referred to as A compositions) and following formula 5 shown in following formula 4
Multi-thiol compound (hereinafter referred to as B component) with mercapto (- SH) is reacted and obtained.
[chemical formula 20]
(the R in formula4For the alkyl of carbon number 1~12.R7For hydrogen atom or methyl.)
[chemical formula 21]
(g in formula is 0 or 1, h are 3 or 4, g and h's and be 4.R1For methylene, ethylidene or isopropylidene.R3For first
Base or ethyl.)
On the other hand, for the embodiment 2 shown in the formula 6 Sulfide-containing Hindered (methyl) acrylate derivative, example
Can by formula 4 as described in making shown in there is (methyl) acrylate-based acyclic compound (A compositions) and the institute of following formula 8
The multi-thiol compound (B component) with mercapto (- SH) shown is reacted and obtained.
[chemical formula 22]
(i in formula is 0~2 integer, and j is 4~6 integer, i and j's and be 6.R1For methylene, ethylidene or different
Propylidene.R3For methyl or ethyl.R6For 6 valency functional groups shown in following formula 7.)
[chemical formula 23]
As the acyclic compound (A compositions) shown in the formula 4, methyl acrylate, ethyl acrylate, third can be included
Olefin(e) acid butyl ester, isobutyl acrylate, acrylic acid-2-ethyl caproite, lauryl ester etc..
As the multi-thiol compound (B component) shown in the formula 5 or the formula 8, trimethylolpropane can be included
Three (3-thiopropionates), pentaerythrite four (3-thiopropionate), trimethylolpropane tris (3- mercaptobutylates), three hydroxyl first
Base ethane three (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), dipentaerythritol six (3-thiopropionate) etc..
For A compositions and B component both compositions, (methyl) acrylate-based mercapto with B component of A compositions passes through
Reaction equation shown in following formula 9 is reacted.In addition, X represents hydrogen atom or methyl, Y represents (methyl) acryloyl with A compositions
Residue beyond the X of the double bond bonding of base, Z represents the residue with the thiol group of B component.
[chemical formula 24]
As shown in Equation 9, the S that two carbon of (methyl) of formation A compositions acrylate-based double bond can be with mercapto
It is bonded, the generation ratio of two kinds of products is different because of reaction condition, such as in the catalyst of this reaction, by alkalescence such as amine
In the case that catalyst is added in reaction system, there are many generation products (1), be added to by radical initiator
In the case of in reaction system, then there are many generation products (2).In most cases, the propylene of the Sulfide-containing Hindered after manufacture
Acid derivative is product (1) and the mixture of (2).
In order to manufacture (methyl) acrylate derivative of Sulfide-containing Hindered, A compositions and temperature of the B component more than 5 DEG C only need to be made
Degree is lower to be reacted, and preferably reacts it at 60~100 DEG C.If being reacted more than 60 DEG C, it can enter in a short time
Row reaction.On the other hand, in the case of reacting at a temperature of more than 100 DEG C, due to polymerizeing mutually between A compositions, nothing
Method only obtains (methyl) acrylate derivative as the Sulfide-containing Hindered of purpose product, so it is not preferred.Further, if anti-
Answer and base catalyst or radical initiator are added in system, then can not only be reacted in shorter time, while can also
Improve the yield of (methyl) acrylate derivative of Sulfide-containing Hindered.
As base catalyst, preferred amine base catalyst, can use primary amine class, secondary amine class or tertiary amines or
Glyoxaline compound.For example, as primary amine, methylamine, ethamine, propylamine, butylamine, ethylenediamine etc. can be included.As secondary amine, it can arrange
Enumerate dimethylamine, diethylamine, di-n-propylamine, Methylethyl amine, diphenylamines etc..As tertiary amine, can include trimethylamine, triethylamine,
Tripropyl amine (TPA), triphenylamine, 1,8- diazabicyclos [5.4.0] 11-amino methyl) phenol etc..As glyoxaline compound, for example
The imidazoles homologys such as 1- methylimidazoles, DMIZ 1,2 dimethylimidazole, 1,4- dimethyl -2- ethyl imidazol(e)s, 1- phenylimidazoles can be included
Thing, the alkyl derivative such as 1- methyl -2- oxygen methylimidazole, 1- methyl -2- oxygen ethyl imidazol(e)s, 1- methyl -4 (5)-nitroimidazole,
Nitro and the aminoderivatives such as 1,2- dimethyl -5 (4)-aminooimidazole, benzimidazole, 1- tolimidazoles, 1- methyl-benzyl
Base benzimidazole etc..
As radical initiator, preferably peroxide or azo-compound, as peroxide, for example, it can include
Aoxidize dibenzoyl, t-butyl peroxy -2 ethyl hexanoic acid ester, dilauroyl peroxide etc..As azo-compound, for example, it can arrange
Enumerate azo double (iso- butyronitrile) or 2,2 '-azo double (2- methylbutyronitriles) etc..
In the manufacture method of (methyl) acrylate derivative of these Sulfide-containing Hindereds, although can be under condition of no solvent
Reacted, but at low temperature react in the case of wait wish reduce viscosity in the case of, solvent can also be added and reacted.
Now, preferably not the carbon-carbon double bond acrylate-based with (methyl) or mercapto reaction solvent, such as preferred alcohols, ketone,
Esters.
The alcohols used as solvent can not contain the carbon-carbon double bond reacted with carbon-carbon double bond or mercapto, mercapto,
The functional groups such as epoxy radicals, NCO, carboxyl, sulfonyl, itrile group, halogen atom.It is used as the alcohol for not containing above-mentioned functional group
Class, can include methanol, ethanol, isopropanol, the tert-butyl alcohol, hexanol, propane diols, glycerine, the alkyl ether of ethylene glycol or ester etc..Its
In, boiling point can keep high reaction temperature for more than 80 DEG C of alcohols, so it is preferred that.
The ketone used as solvent can not contain the carbon-carbon double bond reacted with carbon-carbon double bond or mercapto, mercapto,
The functional groups such as epoxy radicals, NCO, carboxyl, sulfonyl, itrile group, halogen atom.It is used as the ketone for not containing above-mentioned functional group
Class, can include acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone etc..Wherein, boiling point is more than 80 DEG C
Ketone can keep high reaction temperature, so it is preferred that.
The esters used as solvent can not contain the carbon-carbon double bond reacted with carbon-carbon double bond or mercapto, mercapto,
The functional groups such as epoxy radicals, NCO, carboxyl, sulfonyl, itrile group, halogen atom.It is used as the ester for not containing above-mentioned functional group
Class, can include ethyl acetate, butyl acetate, ethyl benzoate, propylene glycol acetate etc..Wherein, boiling point is more than 80 DEG C
Esters can keep high reaction temperature, so it is preferred that.
＜ adhesion improvers ＞
By the way that (methyl) acrylate derivative of the Sulfide-containing Hindered of present embodiment is added into coating or bonding agent etc.
In resin combination, it can be made to be improved for the adhesion of both inorganic material and organic material.Therefore, it is possible to direct
Or mix and used as adhesion improver with solvent etc..Particularly can be by being added to epoxy resin, polyurethane tree
Fat, allyl resin, polyimide resin, polyacetylene etc. have in compound of double bond etc., have given play to high adhesion improvement.
The cause of the adhesion improvement of the adhesion improver is the thioether of (methyl) acrylate derivative of Sulfide-containing Hindered
Base.Therefore, it is described for excellent with the adhesion improvement of the base material of thioether group formation chemical bond (chemical affinity is high)
Base material inorganic substrate such as transition metal or its alloy or silicide, phosphide, sulfide or boride, with insatiable hunger
With the organic matter of key (containing aromatic rings), the organic matter with hydroxyl or carboxyl, or handled by plasma or ultraviolet and ozone
Organic matter etc..Specifically, as inorganic substrate, glass, silicon, various metals etc. can be included., can be excellent as organic substrate
Choosing includes polyethylene terephthalate, polybutylene terephthalate (PBT), polyethylene, polypropylene, makrolon, polyamides
Imines, ABS resin, polyvinyl alcohol, vinyl chloride, polyacetals etc..
Relative to resin combinations such as the coating or bonding agent that 100 mass % contain resin component, add as active ingredients
Plus 0.1~80 mass % (methyl) acrylate derivative using the Sulfide-containing Hindered as active ingredient adhesion improver,
High adhesion can then be played.The adhesion improver has the effect that resin flexibility is improved by ester group, resulting painting
Film also has excellent flexibility.
Embodiment
Hereinafter, embodiment and comparative example are enumerated, the present invention is further specifically described.
(embodiment 1-1)]
[synthesis of (methyl) acrylate derivative of Sulfide-containing Hindered]
In with thermometer, mixer, the three-neck flask of drop pump, (the 3- mercaptopropionic acids of 85.9g dipentaerythritols six are added
Ester) (B component), it is warming up to after 60 DEG C, 14.1g butyl acrylates (A compositions) was added dropwise with 1 hour.After being added dropwise to complete, further exist
Stirring reacts it in 2 hours at 60 DEG C, obtains (methyl) acrylate derivative (synthetic 1) of Sulfide-containing Hindered.
(embodiment 1-2~1-6)
Then, in embodiment 1-2~1-6, in addition to using the A compositions and B component described in table 1 below, with reality
Apply (methyl) acrylate derivative (synthetic 2~6) that a 1-1 synthesizes Sulfide-containing Hindered in the same manner.In addition, the A compositions and B that use
Composition is as follows：
＜ A compositions：Acyclic compound ＞
A-1：Butyl acrylate
A-2：Isobutyl acrylate
A-3：Lauryl ester
A-4：Acrylic acid-2-ethyl caproite
＜ B components：Multi-thiol compound ＞
B-1：Dipentaerythritol six (3-thiopropionate)
B-2：Trimethylolpropane tris (3-thiopropionate)
B-3：Pentaerythrite four (3-thiopropionate)
[table 1]
[infrared absorption spectrum analyzes (IR)]
For the synthetic 1~6 of gained, infrared absorption spectrum analysis (IR) is carried out with following conditions.Its IR spectrum is such as
Shown in Fig. 1~6, while representational IR peaks are as follows.
Kinds of machine：(strain) ST Japan TRavel IR
Decompose：8cm-1, cumulative number：32 times
Embodiment 1-1 (synthetic 1)：Fig. 1
2960cm-1：99%T, 2898cm-1：99%T, 1733cm-1：80%T, 1466cm-1：98%T, 1389cm-1：
96%T, 1355cm-1：94%T, 1289cm-1：96%T, 1243cm-1：90%T, 1150cm-1：84%T, 1054cm-1：95%
T, 1015cm-1：95%T, 938cm-1：96%T, 895cm-1：97%T, 868cm-1：97%T, 837cm-1：97%T, 803cm-1：
97%T, 777cm-1：98%T
Embodiment 1-2 (synthetic 2)：Fig. 2
2960cm-1：99%T, 1732cm-1：80%T, 1470cm-1：97%T, 1385cm-1：96%T, 1354cm-1：
95%T, 1289cm-1：96%T, 1243cm-1：90%T, 1153cm-1：84%T, 1054cm-1：95%T, 1011cm-1：94%
T, 938cm-1：96%T, 907cm-1：97%T, 864cm-1：97%T, 837cm-1：98%T, 822cm-1：97%T, 791cm-1：
98%T, 760cm-1：98%T
Embodiment 1-3 (synthetic 3)：Fig. 3
2925cm-1：97%T, 2856cm-1：99%T, 1737cm-1：83%T, 1466cm-1：98%T, 1412cm-1：
97%T, 1389cm-1：97%T, 1354cm-1：95%T, 1289cm-1：96%T, 1243cm-1：91%T, 1189cm-1：90%
T, 1153cm-1：87%T, 1050cm-1：96%T, 1007cm-1：96%T, 934cm-1：97%T, 891cm-1：97%T, 864cm-1：97%T, 826cm-1：98%T, 760cm-1：98%T
Embodiment 1-4 (synthetic 4)：Fig. 4
2956cm-1：98%T, 2933cm-1：98%T, 2871cm-1：99%T, 1737cm-1：82%T, 1632cm-1：
99%T, 1466cm-1：97%T, 1389cm-1：96%T, 1355cm-1：95%T, 1289cm-1：96%T, 1243cm-1：90%
T, 1154cm-1：95%T, 1011cm-1：95%T, 934cm-1：97%T, 868cm-1：97%T, 826cm-1：97%T, 795cm-1：97%T, 776cm-1：97%T
Embodiment 1-5 (synthetic 5)：Fig. 5
2960cm-1：98%T, 1733cm-1：81%T, 1463cm-1：97%T, 1416cm-1：97%T, 1389cm-1：
96%T, 1355cm-1：95%T, 1243cm-1：90%T, 1150cm-1：86%T, 1057cm-1：96%T, 1019cm-1：96%
T, 938cm-1：97%T, 880cm-1：97%T, 860cm-1：97%T, 837cm-1：97%T, 783cm-1：97%T
Embodiment 1-6 (synthetic 6)：Fig. 6
2964cm-1：99%T, 1733cm-1：80%T, 1470cm-1：98%T, 1412cm-1：96%T, 1389cm-1：
96%T, 1355cm-1：94%T, 1289cm-1：96%T, 1243cm-1：89%T, 1150cm-1：83%T, 1053cm-1：95%
T, 1019cm-1：95%T, 934cm-1：96%T, 876cm-1：97%T, 852cm-1：97%T, 818cm-1：98%T, 799cm-1：
98%T, 783cm-1：98%T
From the infrared absorption spectrum analyze result be clear that, due to do not observe from C=C 1600~
1680cm-1Peak, it will be appreciated that in each synthetic, A compositions are reacted with B component.
[nuclear magnetic resonance spectroscopy (1H-NMR)]
For the synthetic 1~6 obtained in embodiment 1-1~1-6, NMR spectrum point is carried out in following conditions
Analysis.Its result as shown in Fig. 7~12, meanwhile, the structure for each synthetic that the ownership at the peak in each spectrum and its parsing are obtained is such as
Shown in lower.
Kinds of machine：Japanese Bruker (strain) system, 400MHz-Advance400
Cumulative number：32 times
Solvent：Weight chloroform
Standard：TMS
Embodiment 1-1 (synthetic 1)：Fig. 7
[chemical formula 25]
o：0.7~0.9ppm, n：1.2~1.5ppm, a, m：1.5~1.7ppm, b, c, h, i, j, k：2.4~3.0ppm,
e、f：3.2~3.5ppm, d, g, l：3.9~4.2ppm
Embodiment 1-2 (synthetic 2)：Fig. 8
[chemical formula 26]
n、o：0.7~1.0ppm, a：1.5~1.7ppm, m：1.8~2.0ppm, b, c, h, i, j, k：2.4~3.0ppm,
e、f：3.2~3.5ppm, l：3.7~3.9ppm, d, g：3.9~4.3ppm
Embodiment 1-3 (synthetic 3)：Fig. 9
[chemical formula 27]
w：0.7~0.9ppm, n, o, p, q, r, s, t, u, v：1.0~1.4ppm, a, m：1.4~1.7ppm, b, c, h, i,
j、k：2.4~3.0ppm, e, f：3.2~3.5ppm, d, g, l：3.8~4.2ppm
Embodiment 1-4 (synthetic 4)：Figure 10
[chemical formula 28]
q、s：0.7~1.0ppm, n, o, p, r：1.1~1.4ppm, a, m：1.4~1.8ppm, b, c, h, i, j, k：2.3~
3.0ppm, e, f：3.0~3.7ppm, d, g, l：3.8~4.2ppm
Embodiment 1-5 (synthetic 5)：Figure 11
[chemical formula 29]
o、f：0.7~1.0ppm, a, e, m, n：1.2~1.7ppm, b, c, h, i, j, k：2.4~3.0ppm, d, g, l：3.8
~4.2ppm
Embodiment 1-6 (synthetic 6)：Figure 12
[chemical formula 30]
m：0.7~1.0ppm, a, k, l：1.1~1.7ppm, b, c, f, g, h, i：2.4~2.9ppm, d, e, j：3.8~
4.3ppm
From the point of view of Fig. 7~12 and the ownership, do not observe and come from-CH=C (CH near 5.0~5.8ppm3)-
Peak, it may thus be appreciated that A compositions are reacted with B component in each synthetic.
(embodiment 2-1)
2 matter of mixing into the phenol novolak type epoxy resin [Dongdu chemical conversion (strain) system, YDPN638] in 98 mass %
Measure % catalyst [imidazole type catalyst：(strain) ADEKA systems, EH-4344S] resin combination (C-1) in, mix 80 matter
The % synthetic 1 as adhesion improver is measured, its performance is evaluated by following test methods.Evaluation result such as table 2 below
It is shown.
(embodiment 2-2~2-6, comparative example 2-1~2-7)
Then, in embodiment 2-2~2-6, as adhesion improver, except using the synthesis described in table 2 below
Beyond thing 2~6, with embodiment 2-1 identical modes, resin combination (C-1) is mixed with synthetic 2~6, its property is evaluated
Energy.Further, in comparative example 2-1~2-7, as adhesion improver, except using the A compositions or B component described in table 2
Or beyond unreacted A compositions and B component, in the same manner as embodiment 2-1, by resin combination (C-1) and A compositions and B component
At least one of mixed, evaluate its performance.Its result is as described in Table 2.In addition, the unit of the numerical value in table 2 is
Quality %.
＜ test methods ＞
[making of evaluation test film]
On wide 25mm PET film [eastern beautiful (strain) system, Lumirror U46-100], with rod coater by each embodiment
And the mixture obtained in comparative example is coated into 100 microns of thickness, the PET film is overlapped onto to after on base material, with 150
DEG C, the condition of 1 hour solidify it, obtain evaluation test film.
[adhesion 1]
After the evaluation test film is stood into 24 hours at 25 DEG C, used and provided in JIS K6854-3 within 5 minutes
T-shaped stripping method be measured, evaluate it is as follows.
○：Tensile strength is more than 5N/mm (comprising PET fractures)
×：Tensile strength is less than 5N/mm
[adhesion 2]
After the evaluation test film is stood into 24 hours at -10 DEG C, used and advised in JIS K6854-3 within 5 minutes
Fixed T-shaped stripping method is measured, and is evaluated as follows.
○：Tensile strength is more than 5N/mm (comprising PET fractures)
×：Tensile strength is less than 5N/mm
[flexibility]
After the evaluation test film is stood into 24 hours at -10 DEG C, with diameter 8mm rod winding 1 within 5 minutes
Minute, observed, evaluated as follows by visual observation.
○：0 Crack
×：More than 1 crackle
[storage stability]
After resin combination (C-1) is mixed with adhesion improver, the viscosity at 25 DEG C is determined at once (after mixing
Viscosity), while at 40 DEG C heat 12 hours after, again determine viscosity (viscosity after heating), with the viscosity after heating
Divided by mixed viscosity, thickening rate is calculated, is evaluated as follows.In addition, viscosity is the R by using Toki Sangyo Co., Ltd.
Type viscosimeter, is measured under the following conditions.
Use rotor：1°34′×R24
Measurement range：0.5183~103.7PaS
○：Thickening rate 1.0~5.0
×：Thickening rate is less than 1.0 or more than 5.0
[table 2]
It is clear that according to embodiment 2-1~2-6 result, if A compositions will be made to be used with the synthetic obtained by B component reaction
Make adhesion improver, then the adhesion (adhesion 1) of film not only under normal temperature condition is excellent, attaching under cold conditions
Property (adhesion 2), flexibility are also excellent, and can realize the excellent storage stability of resin combination.On the other hand, due to
Adhesion improver is not contained in comparative example 2-1, therefore has no the improvement of adhesion and flexibility.It is evident that in comparative example
In 2-2,2-3,2-7, if A compositions are used alone or are used together in the case of unreacted with B component, although flexibility is obtained
Improvement has been arrived, but it is unconfirmed to adhesion improvement.In addition, the result from comparative example 2-4,2-5,2-6,2-7 is clear that,
B component will be used alone or be used together in the case of unreacted with A compositions, then can not obtain adhesion under cold conditions
Improvement.In addition, in the comparative example 2-7 that B component and A compositions be not reacted to be used, storage stability reduction.From above-mentioned
As a result it is clear that, only by making A compositions enter to react with B component, can obtains and effectively play attaching under cold conditions
The material of property improver performance.
Claims (5)
1. (methyl) acrylate derivative of the Sulfide-containing Hindered shown in following formula 1,
[chemical formula 1]
A in formula is 1~3 integer, the integer that b be 0 or 1, c be 1~3, a and b and c's and be 4；R1For methylene, ethylidene
Or isopropylidene；R2For the divalent functional group shown in following formula 2 or following formula 3；R3For methyl or ethyl；R4For carbon number 1~
12 alkyl,
[chemical formula 2]
R in formula5For methyl,
[chemical formula 3]
R in formula5For methyl.
2. (methyl) acrylate derivative of Sulfide-containing Hindered as claimed in claim 1, the derivative is as third shown in following formula 4
Olefin(e) acid compound is formed with the multi-thiol compound reaction shown in following formula 5,
[chemical formula 4]
R in formula4For the alkyl of carbon number 1~12；R7For methyl,
[chemical formula 5]
G in formula is 0 or 1, h are 3 or 4, g and h's and be 4；R1For methylene, ethylidene or isopropylidene；R3For methyl or second
Base.
3. (methyl) acrylate derivative of the Sulfide-containing Hindered shown in following formula 6,
[chemical formula 6]
D in formula is 1~5 integer, and e is 0~2 integer, and f is 1~5 integer, d and e and f's and be 6；R1For methylene,
Ethylidene or isopropylidene；R2For the divalent functional group shown in following formula 2 or following formula 3；R3For methyl or ethyl；R4For carbon atom
The alkyl of number 1~12；R6For 6 valency functional groups shown in following formula 7,
[chemical formula 7]
R in formula5For hydrogen atom or methyl,
[chemical formula 8]
R in formula5For hydrogen atom or methyl,
[chemical formula 9]
4. (methyl) acrylate derivative of Sulfide-containing Hindered as claimed in claim 3, the derivative is as third shown in following formula 4
Olefin(e) acid compound is formed with the multi-thiol compound reaction shown in following formula 8,
[chemical formula 10]
R in formula4For the alkyl of carbon number 1~12；R7For hydrogen atom or methyl,
[chemical formula 11]
I in formula is 0~2 integer, and j is 4~6 integer, i and j's and be 6；R1For methylene, ethylidene or isopropylidene；
R3For methyl or ethyl；R6For 6 valency functional groups shown in following formula 7,
[chemical formula 12]
5. a kind of adhesion improver, it is spread out with (methyl) acrylate of Sulfide-containing Hindered according to any one of claims 1 to 4
Biology is active ingredient.
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