WO2015186617A1 - Thioether-containing (meth)acrylate derivative and adhesion improver containing same - Google Patents
Thioether-containing (meth)acrylate derivative and adhesion improver containing same Download PDFInfo
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- WO2015186617A1 WO2015186617A1 PCT/JP2015/065504 JP2015065504W WO2015186617A1 WO 2015186617 A1 WO2015186617 A1 WO 2015186617A1 JP 2015065504 W JP2015065504 W JP 2015065504W WO 2015186617 A1 WO2015186617 A1 WO 2015186617A1
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- 0 C*(N(C(C)(C)COC(*OC)=O)C(C)(*)COC(*)=O)[Au] Chemical compound C*(N(C(C)(C)COC(*OC)=O)C(C)(*)COC(*)=O)[Au] 0.000 description 4
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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
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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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- 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
- C09D7/63—Additives non-macromolecular organic
Definitions
- the present invention relates to a novel thioether-containing (meth) acrylate derivative suitably used for an adhesion improver or the like.
- an adhesion improver such as a silane coupling agent has been added to the paint for the purpose of improving adhesion (for example, JP-A-7-300491). Issue no.).
- the silane coupling agent decomposes when heated, when used in a mass production line, silicon oxide is deposited in a heating furnace such as an oven, causing contamination.
- the silane coupling agent alone is sufficient in improving the adhesion, and for example, a salt such as titanium or zirconium, an amine such as imidazole, an adhesion assistant such as a phosphate ester or a urethane resin should be added at the same time.
- the addition of the adhesion aid not only leads to an increase in manufacturing man-hours and costs, but also the addition of the adhesion aid deteriorates the storage stability of the paint at room temperature, There was a problem that the hardness decreased.
- JP 2013-249282 A in order to solve the above-mentioned problem, by using a thioether-containing urea derivative having a specific structure as an adhesion improver, adhesion can be improved without an adhesion aid. It is disclosed.
- Japanese Patent Application Laid-Open No. 2001-89568 discloses a photocurable resin composition containing an addition reaction product obtained by adding a polythiol compound or a polyene compound to a silane coupling agent and a photopolymerization initiator, and has excellent adhesive strength. It is disclosed to exert.
- the above thioether-containing urea derivative, or an addition reaction product of a polythiol compound or polyene compound and a silane coupling agent was used as a paint.
- an adhesion improver it has been found that the resulting coating film has poor flexibility and that cracks are likely to occur when the coating film is bent.
- the present invention has been accomplished in view of the above circumstances.
- the purpose is to provide a material that, when added to a paint, exhibits a high effect of improving adhesion to a substrate without an adhesion aid even in cold regions, and the resulting coating film has flexibility. is there.
- the thioether-containing (meth) acrylate derivative has a structure represented by the following formula 1.
- R 1 is a methylene group.
- R 2 is a divalent functional group represented by the following formula 2 or the following formula 3.
- R 3 is a methyl group or an ethyl group, and R 4 is carbon.
- It is a hydrocarbon group having a number of 1 to 12.
- R 5 is a hydrogen atom or a methyl group.
- R 5 is a hydrogen atom or a methyl group.
- the thioether-containing (meth) acrylate derivative having a structure represented by the above formula 1 is preferably obtained by reacting an acrylic compound represented by the following formula 4 with a polyvalent thiol compound represented by the following formula 5.
- R 4 is a hydrocarbon group having 1 to 12 carbon atoms.
- R 7 is a hydrogen atom or a methyl group.
- g is 0 or 1
- h is 3 or 4
- the sum of g and h is 4.
- R 1 is a methylene group, an ethylene group or an isopropylene group.
- R 3 is methyl. Group or ethyl group.
- the thioether-containing (meth) acrylate derivative of the present invention may have a structure represented by the following formula 6.
- d is an integer of 1 to 5
- e is an integer of 0 to 2
- f is an integer of 1 to 5
- R 1 is A methylene group, an ethylene group or an isopropylene group
- R 2 is a divalent functional group represented by the following formula 2 or the following formula 3.
- R 3 is a methyl group or an ethyl group
- R 4 is And a hydrocarbon group having 1 to 12 carbon atoms
- R 6 is a hexavalent functional group represented by the following formula 7.)
- R 5 is a hydrogen atom or a methyl group.
- R 5 is a hydrogen atom or a methyl group.
- the thioether-containing (meth) acrylate derivative having a structure represented by the above formula 6 is preferably formed by reacting an acrylic compound represented by the following formula 4 with a polyvalent thiol compound represented by the following formula 8.
- R 4 is a hydrocarbon group having 1 to 12 carbon atoms.
- R 7 is a hydrogen atom or a methyl group.
- i is an integer of 0 to 2
- j is an integer of 4 to 6, and the sum of i and j is 6.
- R 1 is a methylene group, an ethylene group or an isopropylene group.
- R 3 is a methyl group or an ethyl group
- R 6 is a hexavalent functional group represented by the following formula 7.
- the present invention also provides an adhesion improver comprising any of the above thioether-containing (meth) acrylate derivatives as an active ingredient.
- (meth) acrylate is a concept including both “methacrylate” and “acrylate”.
- XX to XX means “XX or more, XX or less” unless otherwise specified.
- the thioether-containing (meth) acrylate derivative of the present invention when blended in a paint or the like, exhibits a high effect of improving adhesion to a substrate without an adhesion aid, even in a cold environment such as ⁇ 10 ° C., And the obtained coating film has the effect which has a softness
- the above effect is that, in a cold environment, the ester group having a specific carbon chain imparts flexibility to the paint, and this ester group does not prevent the thioether group and the base material from approaching each other. It is considered that the effect of improving the performance is accurately demonstrated.
- Example 3 is an IR spectrum of the compound 1 obtained in Example 1-1.
- 2 is an IR spectrum of the compound 2 obtained in Example 1-2.
- 3 is an IR spectrum of the compound 3 obtained in Example 1-3.
- 4 is an IR spectrum of the compound 4 obtained in Example 1-4. It is an IR spectrum of the compound 5 obtained in Example 1-5.
- It is an IR spectrum of the compound 6 obtained in Example 1-6.
- 1 is a 1 H-NMR spectrum of Compound 1 obtained in Example 1-1.
- 1 is a 1 H-NMR spectrum of Compound 2 obtained in Example 1-2.
- 1 is a 1 H-NMR spectrum of Synthesis Compound 3 obtained in Example 1-3.
- 1 is a 1 H-NMR spectrum of Compound 4 obtained in Example 1-4.
- 1 is a 1 H-NMR spectrum of Compound 5 obtained in Example 1-5.
- 1 is a 1 H-NMR spectrum of Compound 6 obtained in Example 1-6.
- the thioether-containing (meth) acrylate derivative of this embodiment is a compound represented by the following formula 1.
- R 1 is a methylene group.
- R 2 is a divalent functional group represented by the following formula 2 or the following formula 3.
- R 3 is a methyl group or an ethyl group, and R 4 is carbon.
- It is a hydrocarbon group having a number of 1 to 12.
- R 5 is a hydrogen atom or a methyl group.
- R 5 is a hydrogen atom or a methyl group.
- Examples of the hydrocarbon group having 1 to 12 carbon atoms, which is R 4 in the above formula 1, include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group.
- R 1 in the above formula 1 is a methylene group, an ethylene group, an isopropylene group, since the adhesion improving effect is high, an ethylene group, isopropylene group is particularly preferred.
- the thioether-containing (meth) acrylate derivative represented by the above formula 1 exhibits a high effect of improving adhesion to a substrate without an adhesion aid even in an environment of, for example, ⁇ 10 ° C. when blended in a paint or the like. And it is excellent in the effect which provides a softness
- the thioether-containing (meth) acrylate derivative represented by the above formula 1 has higher compatibility with many resins than the thioether-containing (meth) acrylate derivative of Embodiment 2, it can be applied to a wide range of paints. It is usable and highly versatile.
- Embodiment 2 As Embodiment 2 of a thioether containing (meth) acrylate derivative, the compound represented by following formula 6 is mentioned.
- d is an integer of 1 to 5
- e is an integer of 0 to 2
- f is an integer of 1 to 5
- R 1 is A methylene group, an ethylene group or an isopropylene group
- R 2 is a divalent functional group represented by the following formula 2 or the following formula 3.
- R 3 is a methyl group or an ethyl group
- R 4 is And a hydrocarbon group having 1 to 12 carbon atoms
- R 6 is a hexavalent functional group represented by the following formula 7.)
- R 5 is a hydrogen atom or a methyl group.
- R 5 is a hydrogen atom or a methyl group.
- Examples of the hydrocarbon group having 1 to 12 carbon atoms, which is R 4 in the above formula 6, include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group.
- R 1 in the above formula 6 is a methylene group, an ethylene group, or an isopropylene group, and an ethylene group or an isopropylene group is particularly preferable because the effect of improving adhesion is enhanced.
- the thioether-containing (meth) acrylate derivative represented by the above formula 6 has high adhesion only by adding a small amount as an adhesion improver to a resin composition such as a paint or an adhesive even in an environment of ⁇ 10 ° C., for example.
- the film can be imparted with flexibility and flexibility can be imparted to the resulting coating film.
- the thioether-containing (meth) acrylate derivative of Embodiment 1 represented by Formula 1 above is, for example, an acrylic compound having a (meth) acrylate group represented by Formula 4 below (hereinafter referred to as A component) and Formula 5 below. It can be obtained by reacting with a polyvalent thiol compound having a thiol group (—SH) represented (hereinafter referred to as B component).
- a component an acrylic compound having a (meth) acrylate group represented by Formula 4 below
- B component a polyvalent thiol compound having a thiol group represented
- R 4 is a hydrocarbon group having 1 to 12 carbon atoms.
- R 7 is a hydrogen atom or a methyl group.) (In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is methyl. Group or ethyl group.)
- the thioether-containing (meth) acrylate derivative of Embodiment 2 represented by the above formula 6 is represented by, for example, an acrylic compound (A component) having a (meth) acrylate group represented by the above formula 4 and the following formula 8. It can be obtained by reacting with a polyvalent thiol compound (component B) having a thiol group (—SH).
- component B having a thiol group (—SH).
- i is an integer of 0 to 2
- j is an integer of 4 to 6, and the sum of i and j is 6.
- R 1 is a methylene group, an ethylene group or an isopropylene group.
- R 3 is a methyl group or an ethyl group
- R 6 is a hexavalent functional group represented by the following formula 7.
- acrylic compound (component A) represented by the above formula 4 examples include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and the like.
- the (meth) acrylate group of the A component and the thiol group of the B component react by the reaction formula represented by the following formula 9.
- X represents a hydrogen atom or a methyl group
- Y represents a residue other than X bonded to the double bond of the (meth) acryloyl group of the A component
- Z represents a residue bonded to the thiol group of the B component.
- both of the two carbons forming the double bond of the (meth) acrylate group of the A component can be bonded to S of the thiol group.
- the ratio of the two products varies depending on the reaction conditions. For example, when a basic catalyst such as an amine is added to the reaction system, a large amount of product (1) is produced and the radical generator is reacted. When added to the system, a large amount of product (2) tends to be produced. In many cases, the thioether-containing acrylic derivative after production is a mixture of products (1) and (2).
- the A component and the B component may be reacted at a temperature of 5 ° C. or higher, preferably 60 to 100 ° C.
- the reaction can be performed in a short time.
- the reaction is carried out at a temperature exceeding 100 ° C., polymerization of the A components begins to occur, and only the desired thioether-containing (meth) acrylate derivative cannot be obtained.
- a basic catalyst or a radical generator is added to the reaction system, the reaction can proceed in a shorter time and the yield of the thioether-containing (meth) acrylate derivative can be increased.
- amine-based basic catalysts are preferable, and primary, secondary or tertiary amines, or imidazole compounds can be used.
- the primary amine include methylamine, ethylamine, propylamine, butylamine, and ethylenediamine.
- Secondary amines include dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine and the like.
- Tertiary amines include trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5.4.0) undec-aminomethyl) phenol, and the like.
- imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, imidazole analogues such as 1-phenylimidazole, 1-methyl-2-oxymethylimidazole, Alkyl derivatives such as 1-methyl-2-oxyethylimidazole, nitro and amino derivatives such as 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-5 (4) -aminoimidazole, benzimidazole, 1 -Methylbenzimidazole, 1-methyl-benzylbenzimidazole and the like.
- a peroxide or an azo compound is preferable.
- the peroxide include dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and dilauroyl peroxide.
- the azo compound include azobis (iso-butyronitrile) and 2,2'-azobis (2-methylbutanenitrile).
- the reaction can be allowed to proceed even without a solvent.
- the reaction can be performed by adding a solvent.
- a solvent that does not react with the carbon-carbon double bond of the (meth) acrylate group or the thiol group for example, alcohols, ketones, and esters is preferable.
- Alcohols used as solvents react with carbon-carbon double bonds and thiol groups, such as carbon-carbon double bonds, thiol groups, epoxy groups, isocyanate groups, carboxyl groups, sulfonyl groups, nitrile groups, and halogen atoms. Must not contain groups.
- Examples of alcohols that do not contain the above functional group include methanol, ethanol, isopropyl alcohol, tertiary butanol, hexanol, propylene glycol, glycerin, and alkyl ethers and esters of ethylene glycol.
- alcohols having a boiling point of 80 ° C. or higher are preferable because the reaction temperature can be kept high.
- Ketones used as solvents react with carbon-carbon double bonds and thiol groups, such as carbon-carbon double bonds, thiol groups, epoxy groups, isocyanate groups, carboxyl groups, sulfonyl groups, nitrile groups, and halogen atoms.
- Examples of the ketones that do not contain the functional group include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone. Of these, ketones having a boiling point of 80 ° C. or higher are preferable because the reaction temperature can be kept high.
- Esters used as solvents react with carbon-carbon double bonds and thiol groups, such as carbon-carbon double bonds, thiol groups, epoxy groups, isocyanate groups, carboxyl groups, sulfonyl groups, nitrile groups, and halogen atoms. Must not contain groups.
- ketones that do not contain the above functional group include ethyl acetate, butyl acetate, ethyl benzoate, and propylene glycol acetate. Of these, esters having a boiling point of 80 ° C. or higher are preferable because the reaction temperature can be kept high.
- ⁇ Adhesion improver> By blending the thioether-containing (meth) acrylate derivative of this embodiment into a resin composition such as a paint or an adhesive, adhesion to both inorganic materials and organic materials can be improved. Therefore, it can be used as an adhesion improver as it is or after blending with a solvent or the like. In particular, by blending with a compound having a double bond such as an epoxy resin, a urethane resin, an acrylic resin, a polyimide resin, or polyacetylene, a high effect of improving adhesion can be exhibited.
- the adhesion improving effect of the adhesion improving agent is attributed to the thioether group of the thioether-containing (meth) acrylate derivative.
- a substrate that forms a chemical bond with a thioether group for example, an inorganic substrate such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound, It is excellent in the effect of improving adhesion to an organic substance having a saturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone.
- examples of the inorganic base material include glass, silicon, and various metals.
- Preferred examples of the organic substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride, and polyacetal.
- An adhesion improver comprising the thioether-containing (meth) acrylate derivative as an active ingredient is added in an amount of 0.1 to 80% by weight as an active ingredient with respect to 100% by weight of a resin composition such as a paint or adhesive containing the resin component. High adhesion can be exhibited.
- This adhesion improver also has the effect of increasing the flexibility of the resin by the ester group, and the resulting coating film has excellent flexibility.
- Example 1-1 Synthesis of thioether-containing (meth) acrylate derivatives
- Example 1-2 to 1-6 Next, in Examples 1-2 to 1-6, except that the A component and the B component described in Table 1 below were used, a thioether-containing (meth) acrylate derivative ( Synthesis products 2 to 6) were synthesized.
- the A component and B component which were used are as follows.
- ⁇ A component Acrylic compound> A-1: Butyl acrylate A-2: Isobutyl acrylate A-3: Dodecyl acrylate A-4: 2-ethylhexyl acrylate ⁇ B component: polyvalent thiol compound> B-1: Dipentaerythritol hexakis (3-mercaptopropionate) B-2: Trimethylolpropane tris (3-mercaptopropionate) B-3: Pentaerythritol tetrakis (3-mercaptopropionate)
- Example 1-1 (Compound 1): FIG. 2960 cm ⁇ 1 : 99% T, 2898 cm ⁇ 1 : 99% T, 1733 cm ⁇ 1 : 80% T, 1466 cm ⁇ 1 : 98% T, 1389 cm ⁇ 1 : 96% T, 1355 cm ⁇ 1 : 94% T, 1289 cm ⁇ 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
- Example 1-2 (Compound 2): FIG. 2960 cm ⁇ 1 : 99% T, 1732 cm ⁇ 1 : 80% T, 1470 cm ⁇ 1 : 97% T, 1385 cm ⁇ 1 : 96% T, 1354 cm ⁇ 1 : 95% T, 1289 cm ⁇ 1 : 96% T, 1243 cm ⁇ 1 : 90% T, 1153 cm ⁇ 1 : 84% T, 1054 cm ⁇ 1 : 95% T, 1011 cm ⁇ 1 : 94% T, 938 cm ⁇ 1 : 96% T, 907 cm ⁇ 1 : 97% T, 864 cm ⁇ 1 : 97% T, 837cm -1: 98 % T, 822cm -1: 97% T, 791cm -1: 98% T, 760cm -1: 98% T
- Example 1-3 (Compound 3): FIG. 2925 cm ⁇ 1 : 97% T, 2856 cm ⁇ 1 : 99% T, 1737 cm ⁇ 1 : 83% T, 1466 cm ⁇ 1 : 98% T, 1412 cm ⁇ 1 : 97% T, 1389 cm ⁇ 1 : 97% T, 1354 cm ⁇ 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
- Example 1-4 (Compound 4): FIG. 2956 cm ⁇ 1 : 98% T, 2933 cm ⁇ 1 : 98% T, 2871 cm ⁇ 1 : 99% T, 1737 cm ⁇ 1 : 82% T, 1632 cm ⁇ 1 : 99% T, 1466 cm ⁇ 1 : 97% T, 1389 cm ⁇ 1 : 96% T, 1355 cm ⁇ 1 : 95% T, 1289 cm ⁇ 1 : 96% T, 1243 cm ⁇ 1 : 90% T, 1154 cm ⁇ 1 : 95% T, 1011 cm ⁇ 1 : 95% T, 934 cm ⁇ 1 : 97% T, 868 cm ⁇ 1 : 97% T, 826 cm ⁇ 1 : 97% T, 795 cm ⁇ 1 : 97% T, 776 cm ⁇ 1 : 97% T
- Example 1-5 (Compound 5): FIG. 2960 cm ⁇ 1 : 98% T, 1733 cm ⁇ 1 : 81% T, 1463 cm ⁇ 1 : 97% T, 1416 cm ⁇ 1 : 97% T, 1389 cm ⁇ 1 : 96% T, 1355 cm ⁇ 1 : 95% T, 1243 cm ⁇ 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, 837 cm ⁇ 1 : 97% T, 783 cm ⁇ 1 : 97% T
- Example 1-6 (Compound 6): FIG. 2964 cm ⁇ 1 : 99% T, 1733 cm ⁇ 1 : 80% T, 1470 cm ⁇ 1 : 98% T, 1412 cm ⁇ 1 : 96% T, 1389 cm ⁇ 1 : 96% T, 1355 cm ⁇ 1 : 94% T, 1289 cm ⁇ 1 : 96% T, 1243 cm ⁇ 1 : 89% T, 1150 cm ⁇ 1 : 83% T, 1053 cm ⁇ 1 : 95% T, 1019 cm ⁇ 1 : 95% T, 934 cm ⁇ 1 : 96% T, 876 cm ⁇ 1 : 97% T, 852 cm ⁇ 1 : 97% T, 818 cm ⁇ 1 : 98% T, 799 cm ⁇ 1 : 98% T, 783 cm ⁇ 1 : 98% T
- Example 1-1 (Compound 1): FIG. o: 0.7 to 0.9 ppm, n: 1.2 to 1.5 ppm, a, m: 1.5 to 1.7 ppm, b, c, h, i, j, k: 2.4 to 3. 0 ppm, e, f: 3.2 to 3.5 ppm, d, g, l: 3.9 to 4.2 ppm
- Example 1-2 (Compound 2): FIG. n, o: 0.7 to 1.0 ppm, a: 1.5 to 1.7 ppm, m: 1.8 to 2.0 ppm, b, c, h, i, j, k: 2.4 to 3. 0 ppm, e, f: 3.2 to 3.5 ppm, l: 3.7 to 3.9 ppm, d, g: 3.9 to 4.3 ppm
- Example 1-3 (Compound 3): FIG. w: 0.7 to 0.9 ppm, n, o, p, q, r, s, t, u, v: 1.0 to 1.4 ppm, a, m: 1.4 to 1.7 ppm, b, c, h, i, j, k: 2.4 to 3.0 ppm, e, f: 3.2 to 3.5 ppm, d, g, l: 3.8 to 4.2 ppm
- Example 1-4 (Compound 4): FIG. q, s: 0.7 to 1.0 ppm, n, o, p, r: 1.1 to 1.4 ppm, a, m: 1.4 to 1.8 ppm, b, c, h, i, j, k: 2.3 to 3.0 ppm, e, f: 3.0 to 3.7 ppm, d, g, l: 3.8 to 4.2 ppm
- Example 1-5 (Compound 5): FIG. o, f: 0.7 to 1.0 ppm, a, e, m, n: 1.2 to 1.7 ppm, b, c, h, i, j, k: 2.4 to 3.0 ppm, d, g, l: 3.8 to 4.2 ppm
- Example 1-6 (Compound 6): FIG. m: 0.7 to 1.0 ppm, a, k, l: 1.1 to 1.7 ppm, b, c, f, g, h, i: 2.4 to 2.9 ppm, d, e, j: 3.8 to 4.3 ppm
- Example 2-1 To a resin composition (C-1) obtained by mixing 98% by mass of a phenol novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., YDPN638] with 2% by mass of a catalyst [imidazole type catalyst: Adeka Co., Ltd., EH-4344S]. Then, 80% by mass of Compound 1 was mixed as an adhesion improver, and its performance was evaluated by the following test method. The evaluation results are shown in Table 2 below.
- Example 2-2 to 2-6 Comparative Examples 2-1 to 2-7)
- a resin composition (C) was prepared in the same manner as in Example 2-1, except that the compounds 2 to 6 listed in Table 2 below were used as adhesion improvers. -1) and compounds 2 to 6 were mixed and their performance was evaluated.
- Comparative Examples 2-1 to 2-7 the same procedure as in Example 2-1 was conducted except that the A component or B component shown in Table 2 or the unreacted A component and B component were used as the adhesion improver. Then, the resin composition (C-1) was mixed with at least one of the A component and the B component, and the performance was evaluated. The results are shown in Table 2 below. In addition, the unit of the numerical value in Table 2 is mass%.
- ⁇ Test method> [Create test specimen for evaluation] The mixture obtained in each Example and Comparative Example was applied to a 25 mm wide PET film [Lumirror U46-100, manufactured by Toray Industries, Inc.] with a bar coater to a thickness of 100 microns, and the PET film was applied to the opposing substrate. After the overlapping, it was cured at 150 ° C. for 1 hour to obtain a test piece for evaluation.
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Abstract
Description
(式中のaは1~3の整数であり、bは0または1であり、cは1~3の整数であり、aとbとcの和は4である。R1は、メチレン基、エチレン基またはイソプロピレン基である。R2は、下記式2または下記式3で表される2価の官能基である。R3は、メチル基またはエチル基である。R4は、炭素数が1~12の炭化水素基である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。) According to one characteristic of the present invention, the thioether-containing (meth) acrylate derivative has a structure represented by the following
(Wherein a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a, b and c is 4. R 1 is a methylene group. R 2 is a divalent functional group represented by the following
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
(式中のR4は炭素数が1~12の炭化水素基である。R7は、水素原子またはメチル基である。)
(式中のgは0または1であり、hは3または4であり、gとhの和は4である。R1はメチレン基、エチレン基またはイソプロピレン基である。R3は、メチル基またはエチル基である。) The thioether-containing (meth) acrylate derivative having a structure represented by the
(In the formula, R 4 is a hydrocarbon group having 1 to 12 carbon atoms. R 7 is a hydrogen atom or a methyl group.)
(In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is methyl. Group or ethyl group.)
(式中のdは1~5の整数であり、eは0~2の整数であり、fは1~5の整数であり、dとeとfの和は6である。R1は、メチレン基、エチレン基またはイソプロピレン基である。R2は、下記式2または下記式3で表される2価の官能基である。R3は、メチル基またはエチル基である。R4は、炭素数が1~12の炭化水素基である。R6は下記式7で表される6価の官能基である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。)
(In the formula, d is an integer of 1 to 5, e is an integer of 0 to 2, f is an integer of 1 to 5, and the sum of d, e, and f is 6. R 1 is A methylene group, an ethylene group or an isopropylene group, R 2 is a divalent functional group represented by the following
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
(式中のR4は炭素数が1~12の炭化水素基である。R7は、水素原子またはメチル基である。)
(式中のiは0~2の整数であり、jは4~6の整数であり、iとjの和は6である。R1はメチレン基、エチレン基またはイソプロピレン基である。R3は、メチル基またはエチル基である。R6は、下記式7で表される6価の官能基である。)
(In the formula, R 4 is a hydrocarbon group having 1 to 12 carbon atoms. R 7 is a hydrogen atom or a methyl group.)
(Wherein i is an integer of 0 to 2, j is an integer of 4 to 6, and the sum of i and j is 6. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is a methyl group or an ethyl group, and R 6 is a hexavalent functional group represented by the following formula 7.
<チオエーテル含有(メタ)アクリレート誘導体>
(実施形態1)
本実施形態のチオエーテル含有(メタ)アクリレート誘導体は、下記式1で表される化合物である。
(式中のaは1~3の整数であり、bは0または1であり、cは1~3の整数であり、aとbとcの和は4である。R1は、メチレン基、エチレン基またはイソプロピレン基である。R2は、下記式2または下記式3で表される2価の官能基である。R3は、メチル基またはエチル基である。R4は、炭素数が1~12の炭化水素基である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。) Embodiments that embody the present invention will be described in detail below.
<Thioether-containing (meth) acrylate derivative>
(Embodiment 1)
The thioether-containing (meth) acrylate derivative of this embodiment is a compound represented by the following
(Wherein a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a, b and c is 4. R 1 is a methylene group. R 2 is a divalent functional group represented by the following
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
チオエーテル含有(メタ)アクリレート誘導体の実施形態2として、下記式6で表される化合物が挙げられる。
(式中のdは1~5の整数であり、eは0~2の整数であり、fは1~5の整数であり、dとeとfの和は6である。R1は、メチレン基、エチレン基またはイソプロピレン基である。R2は、下記式2または下記式3で表される2価の官能基である。R3は、メチル基またはエチル基である。R4は、炭素数が1~12の炭化水素基である。R6は下記式7で表される6価の官能基である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。)
As
(In the formula, d is an integer of 1 to 5, e is an integer of 0 to 2, f is an integer of 1 to 5, and the sum of d, e, and f is 6. R 1 is A methylene group, an ethylene group or an isopropylene group, R 2 is a divalent functional group represented by the following
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
上記式1で表される実施形態1のチオエーテル含有(メタ)アクリレート誘導体は、例えば下記式4で表される(メタ)アクリレート基を有するアクリル化合物(以降、A成分という)と、下記式5で表されるチオール基(-SH)を有する多価チオール化合物(以降、B成分という)とを反応させることによって得ることができる。
(式中のR4は炭素数が1~12の炭化水素基である。R7は、水素原子またはメチル基である。)
(式中のgは0または1であり、hは3または4であり、gとhの和は4である。R1はメチレン基、エチレン基またはイソプロピレン基である。R3は、メチル基またはエチル基である。) <Method for producing thioether-containing (meth) acrylate derivative>
The thioether-containing (meth) acrylate derivative of
(In the formula, R 4 is a hydrocarbon group having 1 to 12 carbon atoms. R 7 is a hydrogen atom or a methyl group.)
(In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is methyl. Group or ethyl group.)
(式中のiは0~2の整数であり、jは4~6の整数であり、iとjの和は6である。R1はメチレン基、エチレン基またはイソプロピレン基である。R3は、メチル基またはエチル基である。R6は、下記式7で表される6価の官能基である。)
(Wherein i is an integer of 0 to 2, j is an integer of 4 to 6, and the sum of i and j is 6. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is a methyl group or an ethyl group, and R 6 is a hexavalent functional group represented by the following formula 7.
本実施形態のチオエーテル含有(メタ)アクリレート誘導体は、塗料や接着剤等の樹脂組成物に配合することで、無機材料と有機材料の両方に対する密着性を向上させることができる。そのため、そのままで、あるいは溶剤等と調合して、密着性向上剤として用いることができる。特に、エポキシ樹脂、ウレタン樹脂、アクリル樹脂、ポリイミド樹脂、ポリアセチレンなどの二重結合を有する化合物等に配合することによって、高い密着性向上効果を発揮することができる。この密着性向上剤の密着性向上効果は、チオエーテル含有(メタ)アクリレート誘導体のチオエーテル基に起因している。したがって、チオエーテル基と化学的な結合を形成する(化学的な親和力の高い)基材、例えば、遷移金属あるいはその合金や珪素化合物、リン化合物、硫黄化合物、又はホウ素化合物等の無機基材、不飽和結合(芳香環を含む)を有する有機物、水酸基やカルボキシル基を有する有機物、又はプラズマやUVオゾン処理された有機物等への密着性向上効果に優れる。具体的には、無機基材としては、ガラス、シリコン、各種金属などが挙げられる。有機基材として、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリカーボネート、ポリイミド、ABS樹脂、ポリビニルアルコール、塩化ビニル、ポリアセタールなどが好ましく挙げられる。 <Adhesion improver>
By blending the thioether-containing (meth) acrylate derivative of this embodiment into a resin composition such as a paint or an adhesive, adhesion to both inorganic materials and organic materials can be improved. Therefore, it can be used as an adhesion improver as it is or after blending with a solvent or the like. In particular, by blending with a compound having a double bond such as an epoxy resin, a urethane resin, an acrylic resin, a polyimide resin, or polyacetylene, a high effect of improving adhesion can be exhibited. The adhesion improving effect of the adhesion improving agent is attributed to the thioether group of the thioether-containing (meth) acrylate derivative. Therefore, a substrate that forms a chemical bond with a thioether group (high chemical affinity), for example, an inorganic substrate such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound, It is excellent in the effect of improving adhesion to an organic substance having a saturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone. Specifically, examples of the inorganic base material include glass, silicon, and various metals. Preferred examples of the organic substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride, and polyacetal.
(実施例1-1)
[チオエーテル含有(メタ)アクリレート誘導体の合成]
温度計、攪拌機、滴下ポンプを備えた3つ口フラスコに、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)(B成分)を85.9g仕込み、60℃に昇温後、アクリル酸ブチル(A成分)14.1gを1時間かけて滴下した。滴下終了後さらに60℃で2時間攪拌をして反応させ、チオエーテル含有(メタ)アクリレート誘導体(合成物1)を得た。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
Example 1-1
[Synthesis of thioether-containing (meth) acrylate derivatives]
A three-necked flask equipped with a thermometer, a stirrer, and a dropping pump was charged with 85.9 g of dipentaerythritol hexakis (3-mercaptopropionate) (component B), heated to 60 ° C., and then butyl acrylate ( A component) 14.1g was dripped over 1 hour. After completion of dropping, the mixture was further reacted at 60 ° C. for 2 hours to obtain a thioether-containing (meth) acrylate derivative (Compound 1).
次に、実施例1-2~1-6において、下記表1に記載されたA成分とB成分とを用いた以外は実施例1-1と同様にして、チオエーテル含有(メタ)アクリレート誘導体(合成物2~6)を合成した。なお、用いたA成分及びB成分は次のとおりである。
<A成分:アクリル化合物>
A-1:アクリル酸ブチル
A-2:アクリル酸イソブチル
A-3:アクリル酸ドデシル
A-4:アクリル酸-2-エチルヘキシル
<B成分:多価チオール化合物>
B-1:ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)
B-2:トリメチロールプロパントリス(3-メルカプトプロピオネート)
B-3:ペンタエリスリトールテトラキス(3-メルカプトプロピオネート) (Examples 1-2 to 1-6)
Next, in Examples 1-2 to 1-6, except that the A component and the B component described in Table 1 below were used, a thioether-containing (meth) acrylate derivative (
<A component: Acrylic compound>
A-1: Butyl acrylate A-2: Isobutyl acrylate A-3: Dodecyl acrylate A-4: 2-ethylhexyl acrylate <B component: polyvalent thiol compound>
B-1: Dipentaerythritol hexakis (3-mercaptopropionate)
B-2: Trimethylolpropane tris (3-mercaptopropionate)
B-3: Pentaerythritol tetrakis (3-mercaptopropionate)
得られた合成物1~6ついて、下記条件にて赤外線吸収スペクトル分析(IR)を行った。そのIRスペクトルを図1~6示すとともに、代表的なIRピークを以下に示す。
機種:(株)エス・テイ・ジャパン製 Travel IR
分解:8cm-1、積算回数:32回 [Infrared absorption spectrum analysis (IR)]
The obtained
Model: Travel IR, manufactured by ST Japan
Decomposition: 8 cm −1 , Integration count: 32 times
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 Example 1-1 (Compound 1): FIG.
2960 cm −1 : 99% T, 2898 cm −1 : 99% T, 1733 cm −1 : 80% T, 1466 cm −1 : 98% T, 1389 cm −1 : 96% T, 1355 cm −1 : 94% T, 1289 cm − 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
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 Example 1-2 (Compound 2): FIG.
2960 cm −1 : 99% T, 1732 cm −1 : 80% T, 1470 cm −1 : 97% T, 1385 cm −1 : 96% T, 1354 cm −1 : 95% T, 1289 cm −1 : 96% T, 1243 cm − 1 : 90% T, 1153 cm −1 : 84% T, 1054 cm −1 : 95% T, 1011 cm −1 : 94% T, 938 cm −1 : 96% T, 907 cm −1 : 97% T, 864 cm −1 : 97% T, 837cm -1: 98 % T, 822cm -1: 97% T, 791cm -1: 98% T, 760cm -1: 98% T
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 Example 1-3 (Compound 3): FIG.
2925 cm −1 : 97% T, 2856 cm −1 : 99% T, 1737 cm −1 : 83% T, 1466 cm −1 : 98% T, 1412 cm −1 : 97% T, 1389 cm −1 : 97% T, 1354 cm − 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
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 Example 1-4 (Compound 4): FIG.
2956 cm −1 : 98% T, 2933 cm −1 : 98% T, 2871 cm −1 : 99% T, 1737 cm −1 : 82% T, 1632 cm −1 : 99% T, 1466 cm −1 : 97% T, 1389 cm − 1 : 96% T, 1355 cm −1 : 95% T, 1289 cm −1 : 96% T, 1243 cm −1 : 90% T, 1154 cm −1 : 95% T, 1011 cm −1 : 95% T, 934 cm −1 : 97% T, 868 cm −1 : 97% T, 826 cm −1 : 97% T, 795 cm −1 : 97% T, 776 cm −1 : 97% T
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 Example 1-5 (Compound 5): FIG.
2960 cm −1 : 98% T, 1733 cm −1 : 81% T, 1463 cm −1 : 97% T, 1416 cm −1 : 97% T, 1389 cm −1 : 96% T, 1355 cm −1 : 95% T, 1243 cm − 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, 837 cm −1 : 97% T, 783 cm −1 : 97% T
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 Example 1-6 (Compound 6): FIG.
2964 cm −1 : 99% T, 1733 cm −1 : 80% T, 1470 cm −1 : 98% T, 1412 cm −1 : 96% T, 1389 cm −1 : 96% T, 1355 cm −1 : 94% T, 1289 cm − 1 : 96% T, 1243 cm −1 : 89% T, 1150 cm −1 : 83% T, 1053 cm −1 : 95% T, 1019 cm −1 : 95% T, 934 cm −1 : 96% T, 876 cm −1 : 97% T, 852 cm −1 : 97% T, 818 cm −1 : 98% T, 799 cm −1 : 98% T, 783 cm −1 : 98% T
実施例1-1~1-6で得られた合成物1~6について、下記条件において核磁気共鳴スペクトル分析を行った。その結果を図7~12に示すと共に、各スペクトルにおけるピークの帰属とそれにより解析された各合成物の構造を下記に示す。
機種:日本ブルカー(株)製、400MHz-Advance400
積算回数:32回
溶媒:重クロロホルム
基準:TMS [Nuclear magnetic resonance spectrum analysis ( 1 H-NMR)]
The
Model: Nippon Bruker Co., Ltd., 400MHz-Advanced400
Integration count: 32 times Solvent: Deuterated chloroform Standard: TMS
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 Example 1-1 (Compound 1): FIG.
o: 0.7 to 0.9 ppm, n: 1.2 to 1.5 ppm, a, m: 1.5 to 1.7 ppm, b, c, h, i, j, k: 2.4 to 3. 0 ppm, e, f: 3.2 to 3.5 ppm, d, g, l: 3.9 to 4.2 ppm
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 Example 1-2 (Compound 2): FIG.
n, o: 0.7 to 1.0 ppm, a: 1.5 to 1.7 ppm, m: 1.8 to 2.0 ppm, b, c, h, i, j, k: 2.4 to 3. 0 ppm, e, f: 3.2 to 3.5 ppm, l: 3.7 to 3.9 ppm, d, g: 3.9 to 4.3 ppm
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 Example 1-3 (Compound 3): FIG.
w: 0.7 to 0.9 ppm, n, o, p, q, r, s, t, u, v: 1.0 to 1.4 ppm, a, m: 1.4 to 1.7 ppm, b, c, h, i, j, k: 2.4 to 3.0 ppm, e, f: 3.2 to 3.5 ppm, d, g, l: 3.8 to 4.2 ppm
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 Example 1-4 (Compound 4): FIG.
q, s: 0.7 to 1.0 ppm, n, o, p, r: 1.1 to 1.4 ppm, a, m: 1.4 to 1.8 ppm, b, c, h, i, j, k: 2.3 to 3.0 ppm, e, f: 3.0 to 3.7 ppm, d, g, l: 3.8 to 4.2 ppm
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 Example 1-5 (Compound 5): FIG.
o, f: 0.7 to 1.0 ppm, a, e, m, n: 1.2 to 1.7 ppm, b, c, h, i, j, k: 2.4 to 3.0 ppm, d, g, l: 3.8 to 4.2 ppm
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 Example 1-6 (Compound 6): FIG.
m: 0.7 to 1.0 ppm, a, k, l: 1.1 to 1.7 ppm, b, c, f, g, h, i: 2.4 to 2.9 ppm, d, e, j: 3.8 to 4.3 ppm
フェノールノボラック型エポキシ樹脂[東都化成(株)製、YDPN638]98質量%に触媒[イミダゾール型触媒:(株)アデカ製、EH-4344S]を2質量%混合した樹脂組成物(C-1)へ、密着性向上剤として合成物1を80質量%混合し、下記試験方法によって、その性能を評価した。評価結果を下記表2に示す。 Example 2-1
To a resin composition (C-1) obtained by mixing 98% by mass of a phenol novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., YDPN638] with 2% by mass of a catalyst [imidazole type catalyst: Adeka Co., Ltd., EH-4344S]. Then, 80% by mass of
次に、実施例2-2~2-6において、密着性向上剤として下記表2に記載の合成物2~6を用いた以外は実施例2-1と同様にして、樹脂組成物(C-1)と合成物2~6とを混合し、その性能を評価した。さらに、比較例2-1~2-7において、密着性向上剤として表2に記載のA成分若しくはB成分又は未反応のA成分及びB成分を用いた以外は、実施例2-1と同様にして、樹脂組成物(C-1)とA成分及びB成分の少なくとも一方とを混合し、その性能を評価した。その結果を下記表2に示す。なお、表2中の数値の単位は質量%である。 (Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-7)
Next, in Examples 2-2 to 2-6, a resin composition (C) was prepared in the same manner as in Example 2-1, except that the
[評価用試験片の作成]
各実施例及び比較例で得られた混合物を25mm幅のPETフィルム[東レ(株)製、ルミラーU46-100]上にバーコーターで100ミクロンの厚みに塗布し、対向基材に上記PETフィルムを重ねた後、150℃、1時間の条件で硬化させ評価用試験片を得た。 <Test method>
[Create test specimen for evaluation]
The mixture obtained in each Example and Comparative Example was applied to a 25 mm wide PET film [Lumirror U46-100, manufactured by Toray Industries, Inc.] with a bar coater to a thickness of 100 microns, and the PET film was applied to the opposing substrate. After the overlapping, it was cured at 150 ° C. for 1 hour to obtain a test piece for evaluation.
上記評価用試験片を、25℃で24時間静置した後、5分以内にJIS K6854-3に規定されるT型はく離法で測定し、以下の通り評価した。
○:引っ張り強度が5N/mm以上(PET破断も含む)
×:引っ張り強度が5N/mm未満 [Adhesion 1]
The test piece for evaluation was allowed to stand at 25 ° C. for 24 hours, and was measured within 5 minutes by the T-type peeling method defined in JIS K6854-3, and evaluated as follows.
○: Tensile strength of 5 N / mm or more (including PET fracture)
X: Tensile strength is less than 5 N / mm
上記評価用試験片を、-10℃で24時間静置した後、5分以内にJIS K6854-3に規定されるT型はく離法で測定し、以下の通り評価した。
○:引っ張り強度が5N/mm以上(PET破断も含む)
×:引っ張り強度が5N/mm未満 [Adhesion 2]
The test specimen for evaluation was allowed to stand at −10 ° C. for 24 hours, and was measured within 5 minutes by the T-peeling method defined in JIS K6854-3, and evaluated as follows.
○: Tensile strength of 5 N / mm or more (including PET fracture)
X: Tensile strength is less than 5 N / mm
上記評価用試験片を、-10℃で24時間静置した後、5分以内に直径8mmの棒に1分間巻きつけ、目視にて観察を行い、以下の通り評価した。
○:クラック0本
×:クラック1本以上 [Flexibility]
The test piece for evaluation was allowed to stand at −10 ° C. for 24 hours, and then wound around a rod having a diameter of 8 mm for 1 minute within 5 minutes, visually observed, and evaluated as follows.
○: 0 cracks ×: 1 or more cracks
樹脂組成物(C-1)と密着性向上剤を混合した直後に25℃における粘度(混合後の粘度)を測定するとともに、40℃で12時間加熱した後に再度粘度(加熱後の粘度)を測定し、加熱後の粘度を混合後の粘度で除して増粘率を算出し、以下の通り評価した。なお、粘度は、東機産業株式会社製のR型粘度計を用い、下記条件にて測定した。
使用ロータ:1°34′×R24
測定範囲:0.5183~103.7Pa・s
○:増粘率1.0~5.0
×:増粘率1.0未満、又は5.0超 [Storage stability]
Immediately after mixing the resin composition (C-1) and the adhesion improver, the viscosity at 25 ° C. (viscosity after mixing) is measured, and after heating at 40 ° C. for 12 hours, the viscosity (viscosity after heating) is measured again. Measured, the viscosity after heating was divided by the viscosity after mixing, the thickening rate was calculated, and evaluated as follows. The viscosity was measured under the following conditions using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.
Rotor used: 1 ° 34 '× R24
Measurement range: 0.5183 to 103.7 Pa · s
○: Thickening rate 1.0 to 5.0
X: Thickening rate less than 1.0 or more than 5.0
From the results of Examples 2-1 to 2-6, when a compound obtained by reacting the A component and the B component was used as an adhesion improver, the coating film had adhesion (adhesion properties) under normal temperature conditions. It became clear that not only 1) but also excellent adhesion (coldness 2) and flexibility under cold conditions, and excellent storage stability of the resin composition can be realized. On the other hand, since Comparative Example 2-1 did not contain an adhesion improver, no improvement in adhesion and flexibility was observed. In Comparative Examples 2-2, 2-3, and 2-7, when the component A is used alone or together with the component B without being reacted, the flexibility is improved, but the effect of improving the adhesion is not recognized. It was. In addition, from the results of Comparative Examples 2-4, 2-5, 2-6, and 2-7, even if the B component is used alone or unreacted together with the A component, the effect of improving adhesion can be obtained under cold conditions. It became clear that it was not possible. Moreover, in Comparative Example 2-7 where the B component and the A component were used without reacting, the storage stability was lowered. From these results, it was clarified that a material that effectively functions as an adhesion improver even under cold conditions can be obtained by reacting the A component and the B component.
Claims (5)
- 下記式1で表されるチオエーテル含有(メタ)アクリレート誘導体。
(式中のaは1~3の整数であり、bは0または1であり、cは1~3の整数であり、aとbとcの和は4である。R1は、メチレン基、エチレン基またはイソプロピレン基である。R2は、下記式2または下記式3で表される2価の官能基である。R3は、メチル基またはエチル基である。R4は、炭素数が1~12の炭化水素基である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。) A thioether-containing (meth) acrylate derivative represented by the following formula 1.
(Wherein a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a, b and c is 4. R 1 is a methylene group. R 2 is a divalent functional group represented by the following formula 2 or the following formula 3. R 3 is a methyl group or an ethyl group, and R 4 is carbon. (It is a hydrocarbon group having a number of 1 to 12.)
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.) - 下記式4で表されるアクリル化合物と下記式5で表される多価チオール化合物とを反応させてなる、請求項1に記載のチオエーテル含有(メタ)アクリレート誘導体。
(式中のR4は炭素数が1~12の炭化水素基である。R7は、水素原子またはメチル基である。)
(式中のgは0または1であり、hは3または4であり、gとhの和は4である。R1はメチレン基、エチレン基またはイソプロピレン基である。R3は、メチル基またはエチル基である。) The thioether containing (meth) acrylate derivative of Claim 1 formed by making the polyhydric thiol compound represented by the acrylic compound represented by following formula 4 and the following formula 5 react.
(In the formula, R 4 is a hydrocarbon group having 1 to 12 carbon atoms. R 7 is a hydrogen atom or a methyl group.)
(In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is methyl. Group or ethyl group.) - 下記式6で表されるチオエーテル含有(メタ)アクリレート誘導体。
(式中のdは1~5の整数であり、eは0~2の整数であり、fは1~5の整数であり、dとeとfの和は6である。R1は、メチレン基、エチレン基またはイソプロピレン基である。R2は、下記式2または下記式3で表される2価の官能基である。R3は、メチル基またはエチル基である。R4は、炭素数が1~12の炭化水素基である。R6は下記式7で表される6価の官能基である。)
(R5は水素原子またはメチル基である。)
(R5は水素原子またはメチル基である。)
(In the formula, d is an integer of 1 to 5, e is an integer of 0 to 2, f is an integer of 1 to 5, and the sum of d, e, and f is 6. R 1 is A methylene group, an ethylene group or an isopropylene group, R 2 is a divalent functional group represented by the following formula 2 or the following formula 3. R 3 is a methyl group or an ethyl group, R 4 is And a hydrocarbon group having 1 to 12 carbon atoms, R 6 is a hexavalent functional group represented by the following formula 7.)
(R 5 is a hydrogen atom or a methyl group.)
(R 5 is a hydrogen atom or a methyl group.)
- 下記式4で表されるアクリル化合物と下記式8で表される多価チオール化合物とを反応させてなる、請求項3に記載のチオエーテル含有(メタ)アクリレート誘導体。
(式中のR4は炭素数が1~12の炭化水素基である。R7は、水素原子またはメチル基である。)
(式中のiは0~2の整数であり、jは4~6の整数であり、iとjの和は6である。R1はメチレン基、エチレン基またはイソプロピレン基である。R3は、メチル基またはエチル基である。R6は、下記式7で表される6価の官能基である。)
(In the formula, R 4 is a hydrocarbon group having 1 to 12 carbon atoms. R 7 is a hydrogen atom or a methyl group.)
(Wherein i is an integer of 0 to 2, j is an integer of 4 to 6, and the sum of i and j is 6. R 1 is a methylene group, an ethylene group or an isopropylene group. R 3 is a methyl group or an ethyl group, and R 6 is a hexavalent functional group represented by the following formula 7.
- 請求項1から請求項4のいずれか一項に記載のチオエーテル含有(メタ)アクリレート誘導体を有効成分とする密着性向上剤。 An adhesion improver comprising the thioether-containing (meth) acrylate derivative according to any one of claims 1 to 4 as an active ingredient.
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JP2016132763A (en) * | 2015-01-22 | 2016-07-25 | 日油株式会社 | Curable resin composition |
JP2016138191A (en) * | 2015-01-28 | 2016-08-04 | 日油株式会社 | Curable resin composition |
WO2016190158A1 (en) * | 2015-05-22 | 2016-12-01 | 日油株式会社 | Curable resin composition |
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JP6569410B2 (en) * | 2015-09-10 | 2019-09-04 | 日油株式会社 | Curable resin composition for release sheet, process substrate using the same, and method for protecting substrate |
JP6962009B2 (en) * | 2016-12-09 | 2021-11-05 | 日油株式会社 | Adhesive composition and laminate using it |
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JP2016132763A (en) * | 2015-01-22 | 2016-07-25 | 日油株式会社 | Curable resin composition |
WO2016117454A1 (en) * | 2015-01-22 | 2016-07-28 | 日油株式会社 | Curable resin composition |
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JP2016138191A (en) * | 2015-01-28 | 2016-08-04 | 日油株式会社 | Curable resin composition |
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TWI586728B (en) * | 2015-01-28 | 2017-06-11 | 日油股份有限公司 | Curable resin composition |
WO2016190158A1 (en) * | 2015-05-22 | 2016-12-01 | 日油株式会社 | Curable resin composition |
WO2016190157A1 (en) * | 2015-05-22 | 2016-12-01 | 日油株式会社 | Curable resin composition |
JP2016216641A (en) * | 2015-05-22 | 2016-12-22 | 日油株式会社 | Curable resin composition |
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