CN105339348A - Thioether-containing (meth)acrylate derivative and adhesion improver containing same - Google Patents

Thioether-containing (meth)acrylate derivative and adhesion improver containing same Download PDF

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Publication number
CN105339348A
CN105339348A CN201580000173.6A CN201580000173A CN105339348A CN 105339348 A CN105339348 A CN 105339348A CN 201580000173 A CN201580000173 A CN 201580000173A CN 105339348 A CN105339348 A CN 105339348A
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methyl
formula
following formula
sulfide
integer
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CN105339348B (en
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田代宽
幸田一洋
藤村俊伸
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NOF Corp
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NOF Corp
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a thioether-containing alkoxysilane derivative which has a good adhibition improved effect. The thioether-containing alkoxysilane derivative has a structure represented by formula (1). (In formula (1), a represents an integer of 1-3; b represents 0 or 1; c represents an integer of 1-3; the sum of a, b and c is 4; R1 represents a methylene group, an ethylene group or an isopropylene group; R2 represents a divalent functional group represented by formula (2) or formula (3); R3 represents a methyl group or an ethyl group; and R4 represents a hydrocarbon group having 1-12 carbon atoms.) (In formula (2), R5 represents a hydrogen atom or a methyl group.) (In formula (3), R5 represents a hydrogen atom or a methyl group.)

Description

(methyl) acrylate derivative of Sulfide-containing Hindered and the attaching activator containing this derivative
Technical field
The present invention relates to a kind of (methyl) acrylate derivative being applicable to the novel Sulfide-containing Hindered of attaching property activator etc.
Background technology
In the past, when being coated with various coating on the inorganic substrates such as glass, in order to improve attaching, in coating, add attaching property activator (for example, referring to patent documentation 1) such as silane coupling agent.But there will be following problem, if due to heating silane coupling agent, it decomposes, if use on a production line, then in the process furnace such as baking oven, separates out silicon oxide and forms the reason of pollution.In addition, with regard to independent silane coupling agent, it is abundant that its attaching property not talkative improves effect, such as in most cases, attach property auxiliary agent by the amine, phosphoric acid ester, urethane resin etc. adding the salt of titanium, zirconium etc. or imidazoles etc. simultaneously, the attaching of practical level can be realized.In addition, the interpolation of attaching property auxiliary agent not only relates to the increase of manufacturing process and cost, also exists and causes coating storage stability at room temperature to worsen owing to adding attaching property auxiliary agent, the problem that the thermotolerance of film, hardness reduce.
Patent Document 2 discloses to solve the problem, being used as attaching property activator by the urea derivatives of the Sulfide-containing Hindered using ad hoc structure, even if without attaching property auxiliary agent, also can attaching be improved.
In addition, Patent Document 3 discloses containing the addition reaction of addition poly-thiol compound or polyenic compounds and the Photocurable resin composition of Photoepolymerizationinitiater initiater in silane coupling agent, it has given play to excellent bonding force.
Prior art document
Patent documentation
Patent documentation 1: Unexamined Patent 7-300491 publication
Patent documentation 2: JP 2013-249282 publication
Patent documentation 3: JP 2001-89568 publication
Summary of the invention
The technical problem to be solved in the present invention
But, in cold district, the attaching of coating relative to the film base material with flexibility is studied, its result is known exists following problems: when being used as the attaching activator of coating by the addition reaction of the urea derivatives of described Sulfide-containing Hindered or poly-thiol compound or polyenic compounds and silane coupling agent, the film obtained lacks flexibility, easily cracks when film bends.
The present invention completes in view of above-mentioned actual state, its object is to provide a kind of material, this material when making an addition to coating etc., even if when cold district is without attaching property auxiliary agent, also can play and improve effect relative to the height attaching property of base material, and the film obtained has flexibility.
The technique means of technical solution problem
To achieve these goals, (methyl) acrylate derivative of Sulfide-containing Hindered of the present invention has the structure shown in following formula 1.
[chemical formula 1]
(a in formula is the integer of 1 ~ 3, b be 0 or 1, c be the integer of 1 ~ 3, a and b is with c's and be 4.R 1for methylene radical, ethylidene or isopropylidene.R 2for the divalent functional group shown in following formula 2 or following formula 3.R 3for methyl or ethyl.R 4for the alkyl of carbonatoms 1 ~ 12.)
[chemical formula 2]
(R 5for hydrogen atom or methyl.)
[chemical formula 3]
(R 5for hydrogen atom or methyl.)
There is (methyl) acrylate derivative of the Sulfide-containing Hindered of structure shown in above-mentioned formula 1, preferably reacted by the multi-thiol compound shown in the acrylic compound shown in following formula 4 and following formula 5 and form.
[chemical formula 4]
(the R in formula 4for the alkyl of carbonatoms 1 ~ 12.R 7for hydrogen atom or methyl.)
[chemical formula 5]
(g in formula be 0 or 1, h be 3 or 4, g and h and be 4.R 1for methylene radical, ethylidene or isopropylidene.R 3for methyl or ethyl.)
In addition, (methyl) acrylate derivative of Sulfide-containing Hindered of the present invention also can contain the structure shown in following formula 6.
[chemical formula 6]
(d in formula is the integer of 1 ~ 5, and e is the integer of 0 ~ 2, and f is the integer of 1 ~ 5, and d and e is with f's and be 6.R 1for methylene radical, ethylidene or isopropylidene.R 2for the divalent functional group shown in following formula 2 or following formula 3.R 3for methyl or ethyl.R 4for the alkyl of carbonatoms 1 ~ 12.R 6for 6 valency functional groups shown in following formula 7.)
[chemical formula 7]
(R 5for hydrogen atom or methyl.)
[chemical formula 8]
(R 5for hydrogen atom or methyl.)
[chemical formula 9]
Described (methyl) acrylate derivative with the Sulfide-containing Hindered of the structure shown in formula 6 is preferably reacted by the multi-thiol compound shown in the acrylic compound shown in following formula 4 and following formula 8 and forms.
[chemical formula 10]
(the R in formula 4for the alkyl of carbonatoms 1 ~ 12.R 7for hydrogen atom or methyl.)
[chemical formula 11]
(i in formula is the integer of 0 ~ 2, and j is the integer of 4 ~ 6, i and j's and be 6.R 1for methylene radical, ethylidene or isopropylidene.R 3for methyl or ethyl.R 6for 6 valency functional groups shown in following formula 7.)
[chemical formula 12]
In addition, the present invention also provides a kind of and attaches property activator, its with any one of (methyl) acrylate derivative of described Sulfide-containing Hindered for effective constituent.
In addition, in this manual, " (methyl) acrylate " refers to and comprises " methacrylic ester " and " acrylate " both concepts.In addition, about the record of " 00 ~ ×× " in this specification sheets, record as long as no other, be the meaning of " more than 00, ×× below ".
Invention effect
When (methyl) acrylate derivative of Sulfide-containing Hindered of the present invention being added in coating etc., even if such as under the cold environment of-10 DEG C, also have when improving effect without having given play to the high property that attaches relative to base material when attaching property auxiliary agent, and the film obtained have the effect of flexibility.It is believed that above-mentioned effect is because in cold environments, the ester group with specific carbochain gives coating flexibility, and this ester group does not hinder the close of thioether group and base material, and the attaching therefore having played thioether group generation effectively improves effect.
Accompanying drawing explanation
Fig. 1 is the IR spectrum of the synthetics 1 obtained in embodiment 1-1;
Fig. 2 is the IR spectrum of the synthetics 2 obtained in embodiment 1-2;
Fig. 3 is the IR spectrum of the synthetics 3 obtained in embodiment 1-3;
Fig. 4 is the IR spectrum of the synthetics 4 obtained in embodiment 1-4;
Fig. 5 is the IR spectrum of the synthetics 5 obtained in embodiment 1-5;
Fig. 6 is the IR spectrum of the synthetics 6 obtained in embodiment 1-6;
Fig. 7 is the synthetics 1 obtained in embodiment 1-1 1h-NMR composes;
Fig. 8 is the synthetics 2 obtained in embodiment 1-2 1h-NMR composes;
Fig. 9 is the synthetics 3 obtained in embodiment 1-3 1h-NMR composes;
Figure 10 is the synthetics 4 obtained in embodiment 1-4 1h-NMR composes;
Figure 11 is the synthetics 5 obtained in embodiment 1-5 1h-NMR composes;
Figure 12 is the synthetics 6 obtained in embodiment 1-6 1h-NMR composes.
Embodiment
Below, embodiment the present invention specialized is described in detail.
(methyl) acrylate derivative > of < Sulfide-containing Hindered
(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 the integer of 1 ~ 3, b be 0 or 1, c be the integer of 1 ~ 3, a and b is with c's and be 4.R 1for methylene radical, ethylidene or isopropylidene.R 2for the divalent functional group shown in following formula 2 or following formula 3.R 3for methyl or ethyl.R 4for the alkyl of carbonatoms 1 ~ 12.)
[chemical formula 14]
(R 5for hydrogen atom or methyl.)
[chemical formula 15]
(R 5for hydrogen atom or methyl.)
As the R in described formula 1 4the alkyl of carbonatoms 1 ~ 12, straight chained alkyl, the alkyl with side chain, cyclic alkyl can be listed.R in described formula 1 1for methylene radical, ethylidene, isopropylidene, improve effect, particularly preferably ethylidene, isopropylidene from raising attaching property.
When (methyl) acrylate derivative of the Sulfide-containing Hindered shown in described formula 1 being added in coating etc., even if such as under the environment of-10 DEG C, also there is following excellent effect: given play to the high property that attaches when nothing attaching property auxiliary agent relative to base material and improved effect and give obtained soft film coating.Further, (methyl) acrylate derivative of the Sulfide-containing Hindered shown in described formula 1 is less than the molecular weight of (methyl) acrylate derivative of the Sulfide-containing Hindered of embodiment 2 described later, and thus solvability is excellent.Therefore, for most resin, (methyl) acrylate derivative of Sulfide-containing Hindered shown in described formula 1 has the intermiscibility higher than (methyl) acrylate derivative of the Sulfide-containing Hindered of embodiment 2, therefore can to coating use widely, and versatility is high.
(embodiment 2)
As the embodiment 2 of (methyl) acrylate derivative of Sulfide-containing Hindered, the compound shown in following formula 6 can be listed.
[chemical formula 16]
(d in formula is the integer of 1 ~ 5, and e is the integer of 0 ~ 2, and f is the integer of 1 ~ 5, and d and e is with f's and be 6.R 1for methylene radical, ethylidene or isopropylidene.R 2for the divalent functional group shown in following formula 2 or following formula 3.R 3for methyl or ethyl.R 4for the alkyl of carbonatoms 1 ~ 12.R 6for 6 valency functional groups shown in following formula 7.)
[chemical formula 17]
(R 5for hydrogen atom or methyl.)
[chemical formula 18]
(R 5for hydrogen atom or methyl.)
[chemical formula 19]
As the R in described formula 6 4carbonatoms be the alkyl of 1 ~ 12, straight chained alkyl, the alkyl with side chain, cyclic alkyl can be listed.R in described formula 6 1for methylene radical, ethylidene, isopropylidene, improve effect from raising attaching property, be particularly preferably ethylidene, isopropylidene.
For (methyl) acrylate derivative of the Sulfide-containing Hindered shown in described formula 6, even if such as under the cold environment of-10 DEG C, as long as make an addition on a small quantity in the resin combination of coating or caking agent etc. as attaching property activator, just can give their high attaching property, and the film that imparting obtains is with flexibility.
The manufacture method > of (methyl) acrylate derivative of < Sulfide-containing Hindered
For (methyl) acrylate derivative of the Sulfide-containing Hindered of the embodiment 1 shown in described formula 1, such as, by making the multi-thiol compound (hereinafter referred to as B component) with thiol group (-SH) shown in (methyl) acrylate-based acrylic compound (hereinafter referred to as A composition) Yu following formula 5 that has shown in following formula 4 carry out reacting and obtain.
[chemical formula 20]
(the R in formula 4for the alkyl of carbonatoms 1 ~ 12.R 7for hydrogen atom or methyl.)
[chemical formula 21]
(g in formula be 0 or 1, h be 3 or 4, g and h and be 4.R 1for methylene radical, ethylidene or isopropylidene.R 3for methyl or ethyl.)
On the other hand, for (methyl) acrylate derivative of the Sulfide-containing Hindered of the embodiment 2 shown in described formula 6, such as, can be undertaken reacting by making the multi-thiol compound (B component) with thiol group (-SH) shown in (methyl) acrylate-based acrylic compound (A composition) Yu following formula 8 that has shown in described formula 4 and obtain.
[chemical formula 22]
(i in formula is the integer of 0 ~ 2, and j is the integer of 4 ~ 6, i and j's and be 6.R 1for methylene radical, ethylidene or isopropylidene.R 3for methyl or ethyl.R 6for 6 valency functional groups shown in following formula 7.)
[chemical formula 23]
As the acrylic compound (A composition) shown in described formula 4, methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, ethyl acrylate, lauryl ester etc. can be listed.
As the multi-thiol compound (B component) shown in described formula 5 or described formula 8, trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptobutylate), trimethylolethane trimethacrylate (3-mercaptobutylate), tetramethylolmethane four (3-mercaptobutylate), Dipentaerythritol six (3-mercaptopropionic acid ester) etc. can be listed.
For A composition and these two kinds of compositions of B component, (methyl) of A composition is acrylate-based to be reacted by the reaction formula shown in following formula 9 with the thiol group of B component.In addition, X represents hydrogen atom or methyl, Y represent with the X of the double bond bonding of (methyl) acryl of A composition beyond residue, Z represents the residue with the thiol group of B component.
[chemical formula 24]
As shown in Equation 9, two carbon forming the acrylate-based double bond of (methyl) of A composition all can carry out bonding with the S of thiol group, the generation ratio of two kinds of resultants is different because of reaction conditions, such as, in the catalyzer of this reaction, when the basic catalysts such as amine are added in reaction system, there is the tendency generating resultant (1) more, when being added in reaction system by radical initiator, then having the tendency generating resultant (2) more.In most cases, the acrylic acid derivative of the Sulfide-containing Hindered after manufacture is the mixture of resultant (1) and (2).
In order to manufacture (methyl) acrylate derivative of Sulfide-containing Hindered, carrying out reacting under only need making A composition and the temperature of B component more than 5 DEG C, preferably at 60 ~ 100 DEG C, making it react.If react more than 60 DEG C, then can react at short notice.On the other hand, when reacting at the temperature more than 100 DEG C, owing to being polymerized mutually between A composition, (methyl) acrylate derivative of the Sulfide-containing Hindered as object product only cannot be obtained, so not preferred.Further, if add basic catalyst or radical initiator in reaction system, then can not only react in shorter time, the yield of (methyl) acrylate derivative of Sulfide-containing Hindered can also be improved simultaneously.
As basic catalyst, preferred amine basic catalyst, can use primary amine class, secondary amine class or tertiary amines or glyoxaline compound.Such as, as primary amine, methylamine, ethamine, propylamine, butylamine, quadrol etc. can be listed.As secondary amine, dimethylamine, diethylamine, dipropyl amine, methylethyl amine, pentanoic etc. can be listed.As tertiary amine, Trimethylamine 99, triethylamine, tripropyl amine, triphenylamine, 1,8-diazabicyclo [5.4.0] 11-amino methyl can be listed) phenol etc.As glyoxaline compound, include, for example out 1-Methylimidazole, 1,2-methylimidazole, 1, the imidazoles homologues such as 4-dimethyl-2-ethyl imidazol(e), 1-phenylimidazole, the alkyl derivatives such as 1-methyl-2-oxygen Methylimidazole, 1-methyl-2-oxygen ethyl imidazol(e), nitro and the aminoderivatives such as 1-methyl-4 (5)-nitroimidazole, 1,2-dimethyl-5 (4)-aminooimidazole, benzoglyoxaline, 1-tolimidazole, 1-Methyl-benzvl benzoglyoxaline etc.
As radical initiator, preferred superoxide or azo-compound, as superoxide, include, for example out dibenzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, dilauroyl peroxide etc.As azo-compound, include, for example out azo two (iso-butyronitrile) or 2,2 '-azo two (2-methylbutyronitrile) etc.
In the manufacture method of (methyl) acrylate derivative of these Sulfide-containing Hindereds, although can react under condition of no solvent, under low viscous situation falls in the inferior hope of the situation of reacting at low temperatures, also can add solvent and react.Now, the solvent that preferably not acrylate-based with (methyl) carbon-carbon double bond or thiol group react, such as preferred alcohols, ketone, ester class.
The alcohols used as solvent can not contain the functional group such as carbon-carbon double bond, thiol group, epoxy group(ing), isocyanate group, carboxyl, alkylsulfonyl, itrile group, halogen atom of reacting with carbon-carbon double bond or thiol group.As not containing the alcohols of above-mentioned functional group, methyl alcohol, ethanol, Virahol, the trimethyl carbinol, hexanol, propylene glycol, glycerol, the alkyl oxide of ethylene glycol or ester etc. can be listed.Wherein, boiling point is that the alcohols of more than 80 DEG C can keep high temperature of reaction, so preferably.
The ketone used as solvent can not contain the functional group such as carbon-carbon double bond, thiol group, epoxy group(ing), isocyanate group, carboxyl, alkylsulfonyl, itrile group, halogen atom of reacting with carbon-carbon double bond or thiol group.As the ketone not containing above-mentioned functional group, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone etc. can be listed.Wherein, boiling point is that the ketone of more than 80 DEG C can keep high temperature of reaction, so preferably.
The ester class used as solvent can not contain the functional group such as carbon-carbon double bond, thiol group, epoxy group(ing), isocyanate group, carboxyl, alkylsulfonyl, itrile group, halogen atom of reacting with carbon-carbon double bond or thiol group.As the ketone not containing above-mentioned functional group, ethyl acetate, butylacetate, ethyl benzoate, propylene glycol acetate etc. can be listed.Wherein, boiling point is that the ester class of more than 80 DEG C can keep high temperature of reaction, so preferably.
< attaching property activator >
Add in the resin combination of coating or caking agent etc. by (methyl) acrylate derivative of the Sulfide-containing Hindered by present embodiment, its attaching for inorganic materials and organic materials can be made to improve.Therefore, it is possible to directly or mix with solvent etc. and use as attaching property activator.Particularly can have in the compound of double bond etc. by adding epoxy resin, urethane resin, acrylic resin, polyimide resin, polyacetylene etc. to, having given play to the high property that attaches and having improved effect.The cause that the attaching of described attaching activator improves effect is the thioether group of (methyl) acrylate derivative of Sulfide-containing Hindered.Therefore, it improves excellent effect for the attaching forming the base material of chemical bond (chemical affinity is high) with thioether group, described base material such as transition metal or the inorganic substrate such as its alloy or silicide, phosphide, sulfide or boride, there is the organism of unsaturated link(age) (containing aromatic nucleus), there is the organism of hydroxyl or carboxyl, or through the organism etc. of plasma or ultraviolet and ozone process.Specifically, as inorganic substrate, glass, silicon, various metals etc. can be listed.As organic substrate, can preferably list polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinylchlorid, polyacetal etc.
The resin combination such as coating or caking agent of resinous principle is contained relative to 100 quality %, in effective constituent interpolation 0.1 ~ 80 quality % take (methyl) acrylate derivative of described Sulfide-containing Hindered as the attaching activator of effective constituent, then can play highly to attach property.This attaching activator has by the soft effect of ester group raising resin flexible, and the film obtained also has excellent flexibility.
Embodiment
Below, enumerate embodiment and comparative example, specifically describe the present invention further.
(embodiment 1-1)]
[synthesis of (methyl) acrylate derivative of Sulfide-containing Hindered]
There is thermometer, stirrer, dripping in the three-necked flask of pump, add 85.9g Dipentaerythritol six (3-mercaptopropionic acid ester) (B component), after being warming up to 60 DEG C, drip 14.1g butyl acrylate (A composition) with 1 hour.After being added dropwise to complete, stirring at 60 DEG C further and make it react in 2 hours, obtain (methyl) acrylate derivative (synthetics 1) of Sulfide-containing Hindered.
(embodiment 1-2 ~ 1-6)
Then, in embodiment 1-2 ~ 1-6, except use in following table 1 record A composition and B component except, synthesize (methyl) acrylate derivative (synthetics 2 ~ 6) of Sulfide-containing Hindered identically with embodiment 1-1.In addition, the A composition of use and B component as follows:
< A composition: acrylic compound >
A-1: butyl acrylate
A-2: isobutyl acrylate
A-3: lauryl ester
A-4: ethyl acrylate
< B component: multi-thiol compound >
B-1: Dipentaerythritol six (3-mercaptopropionic acid ester)
B-2: trimethylolpropane tris (3-mercaptopropionic acid ester)
B-3: tetramethylolmethane four (3-mercaptopropionic acid ester)
[table 1]
[infrared absorption spectrum analysis (IR)]
For the synthetics 1 ~ 6 of gained, carry out infrared absorption spectrum analysis (IR) with following condition.As shown in figs. 1 to 6, representational IR peak is as follows simultaneously for its IR spectrum.
Kinds of machine: (strain) STJapan TRavelIR
Decompose: 8cm -1, cumulative number: 32 times
Embodiment 1-1 (synthetics 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 (synthetics 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 (synthetics 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 (synthetics 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 (synthetics 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 (synthetics 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
The result analyzed from described infrared absorption spectrum clearly, owing to not observing 1600 ~ 1680cm from C=C -1peak, thus known in each synthetics, A composition and B component are reacted.
[nuclear magnetic resonance spectroscopy ( 1h-NMR)]
For the synthetics 1 ~ 6 obtained in embodiment 1-1 ~ 1-6, in following condition, carry out nuclear magnetic resonance spectroscopy.Its result is as shown in Fig. 7 ~ 12, and meanwhile, the structure of each synthetics that the ownership at the peak in each spectrum and parsing thereof obtain is as follows.
Kinds of machine: Japanese Bruker (strain) makes, 400MHz-Advance400
Cumulative number: 32 times
Solvent: heavy chloroform
Standard: TMS
Embodiment 1-1 (synthetics 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 (synthetics 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 (synthetics 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 (synthetics 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 (synthetics 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 (synthetics 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 Fig. 7 ~ 12 and described ownership, do not observe near 5.0 ~ 5.8ppm from-CH=C (CH 3)-peak, therefore known in each synthetics A composition and B component react.
(embodiment 2-1)
To the phenol novolak type epoxy resin at 98 quality %, [Dongdu changes into (strain) makes, YDPN638] middle catalyzer [the imidazole type catalyzer: (strain) ADEKA system mixing 2 quality %, EH-4344S] resin combination (C-1) in, mix the synthetics 1 as attaching property activator of 80 quality %, evaluate its performance by following test method.Evaluation result as described in Table 2.
(embodiment 2-2 ~ 2-6, comparative example 2-1 ~ 2-7)
Then, in embodiment 2-2 ~ 2-6, as attaching property activator, except using the synthetics 2 ~ 6 described in following table 2, in the mode identical with embodiment 2-1, resin combination (C-1) is mixed with synthetics 2 ~ 6, evaluate its performance.Further, in comparative example 2-1 ~ 2-7, as attaching property activator, except using A composition described in table 2 or B component or unreacted A composition and B component, in the same manner as embodiment 2-1, resin combination (C-1) is mixed with at least one in A composition and B component, evaluates its performance.Its result as described in Table 2.In addition, the unit of the numerical value in table 2 is quality %.
< test method >
[making of evaluation test film]
In PET film [east beautiful (strain) system that 25mm is wide, LumirrorU46-100] on, with rod coater, the mixture obtained in each embodiment and comparative example is coated into the thickness of 100 microns, described PET film is overlapped onto after on subtend base material, make it solidify with the condition of 150 DEG C, 1 hour, obtain evaluation test film.
[attaching property 1]
After described evaluation test film is left standstill 24 hours at 25 DEG C, measured by the T-shaped stripping method specified in JISK6854-3 within 5 minutes, evaluate as follows.
Zero: tensile strength is more than 5N/mm (comprising PET fracture)
×: tensile strength is less than 5N/mm
[attaching property 2]
After described evaluation test film is left standstill 24 hours at-10 DEG C, measured by the T-shaped stripping method specified in JISK6854-3 within 5 minutes, evaluate as follows.
Zero: tensile strength is more than 5N/mm (comprising PET fracture)
×: tensile strength is less than 5N/mm
[flexibility]
After described evaluation test film is left standstill 24 hours at-10 DEG C, reeled 1 minute with the rod of diameter 8mm within 5 minutes, observed by visual, evaluate as follows.
Zero: 0 Crack
×: more than 1 crackle
[storage stability]
After resin combination (C-1) is mixed with attaching property activator, be determined at the viscosity (mixed viscosity) at 25 DEG C at once, heat at 40 DEG C after 12 hours simultaneously, measure viscosity (viscosity after heating) again, by the viscosity after heating divided by mixed viscosity, calculate thickening rate, evaluate as follows.In addition, viscosity is the R type viscometer by using Toki Sangyo Co., Ltd., measures under the following conditions.
Use rotor: 1 ° of 34 ' × R24
Measurement range: 0.5183 ~ 103.7PaS
Zero: thickening rate 1.0 ~ 5.0
×: thickening rate is less than 1.0 or more than 5.0
[table 2]
Clearly known according to the result of embodiment 2-1 ~ 2-6, if the synthetics making A composition and B component react gained is used as attaching property activator, the then attaching of film not only under normal temperature condition (attaching property 1) is excellent, attaching under cold conditions (attaching property 2), flexibility are also excellent, and can realize the storage stability of the excellence of resin combination.On the other hand, owing to not containing attaching property activator in comparative example 2-1, the improvement of attaching property and flexibility is therefore had no.Be apparent that, in comparative example 2-2,2-3,2-7, if be used alone A composition or together use with B component in unreacted situation, although then flexibility is improved, unconfirmed to attaching property improve effect.In addition, from the result of comparative example 2-4,2-5,2-6,2-7 clearly, B component will be used alone or together use with A composition in unreacted situation, then cannot obtain attaching property under cold conditions and improve effect.In addition, in the comparative example 2-7 that B component and A composition use without reaction, storage stability reduces.From the above results clearly, only having by making A composition and B component enter to react, the material effectively playing attaching property activator performance under cold conditions can be obtained.

Claims (5)

1. (methyl) acrylate derivative of the Sulfide-containing Hindered shown in following formula 1,
A in formula is the integer of 1 ~ 3, b be 0 or 1, c be the integer of 1 ~ 3, a and b is with c's and be 4; R 1for methylene radical, ethylidene or isopropylidene; R 2for the divalent functional group shown in following formula 2 or following formula 3; R 3for methyl or ethyl; R 4for the alkyl of carbonatoms 1 ~ 12,
R in formula 5for hydrogen atom or methyl,
R in formula 5for hydrogen atom or methyl.
2. (methyl) acrylate derivative of Sulfide-containing Hindered as claimed in claim 1, this derivative is reacted by the multi-thiol compound shown in the acrylic compound shown in following formula 4 and following formula 5 and forms,
R in formula 4for the alkyl of carbonatoms 1 ~ 12; R 7for hydrogen atom or methyl,
G in formula be 0 or 1, h be 3 or 4, g and h and be 4; R 1for methylene radical, ethylidene or isopropylidene; R 3for methyl or ethyl.
3. (methyl) acrylate derivative of the Sulfide-containing Hindered shown in following formula 6,
D in formula is the integer of 1 ~ 5, and e is the integer of 0 ~ 2, and f is the integer of 1 ~ 5, and d and e is with f's and be 6; R 1for methylene radical, ethylidene or isopropylidene; R 2for the divalent functional group shown in following formula 2 or following formula 3; R 3for methyl or ethyl; R 4for the alkyl of carbonatoms 1 ~ 12; R 6for 6 valency functional groups shown in following formula 7,
R in formula 5for hydrogen atom or methyl,
R in formula 5for hydrogen atom or methyl,
4. (methyl) acrylate derivative of Sulfide-containing Hindered as claimed in claim 3, this derivative is reacted by the multi-thiol compound shown in the acrylic compound shown in following formula 4 and following formula 8 and forms,
R in formula 4for the alkyl of carbonatoms 1 ~ 12; R 7for hydrogen atom or methyl,
I in formula is the integer of 0 ~ 2, and j is the integer of 4 ~ 6, i and j's and be 6; R 1for methylene radical, ethylidene or isopropylidene; R 3for methyl or ethyl; R 6for 6 valency functional groups shown in following formula 7,
5. attach property an activator, its with (methyl) acrylate derivative of the Sulfide-containing Hindered according to any one of Claims 1 to 4 for effective constituent.
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