Classifications

• • 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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

• the present invention relates to a curable resin composition to be used for resin processing and molding which has decomposability and does not prevent recycling of itself or materials to which it is attached, and a resin to be used for paints, inks, adhesives and the like containing the resin composition.
• the present invention relates to a resin composition to which such method for such removal is applicable.
• a resin composition to which such method for such removal is applicable there is paint where a resin containing a carbonyl group is cured with a dihydrazide compound, for example.
• the paint cannot be applied to the case where crosslinking is not required or where crosslinking is carried out by other means such as light, heat or the like, so that its usable range is limited.
• the present invention relates to a curable composition containing a resin (A) having the structure of the structural formula represented by the formula (1) below:
• the structure of the structural formula represented by formula (1) present in the resin (A) may be formed by the reaction of a carbonyl group with a hydrazide group or a semicarbazide group.
• the crosslinkable functional group (or groups) present in the resin (A) may be one type or two or more types selected from a polymerizable double bond, hydroxyl group, carboxyl group, isocyanate group, amino group, thiol group, epoxy group, triazine group, dimide group, silanol group, an alkoxysilyl group, methylol group, an alkylmethylol group, an acetoalkoxy group, carbonyl group, hydrazide group, a blocked isocyanate group, a blocked carboxyl group and a blocked hydroxyl group.
• the resin (A) may be that having one or more structures of the structural formula represented by the formula (1) between the crosslinkable functional groups.
• the resin may be a resin having the structure of the structural formula represented by formula (1) in the backbone of the resin and the crosslinkable functional group in the side chain.
• the resin (A) may be a resin having the same number of the structure or structures of the structural formula represented by formula (1) and the crosslinkable functional group or groups.
• An organic resin which contains the structure of the structural formula represented by formula (1) and a coexisting crosslinkable functional group may be used as the resin (A).
• the examples of the organic resin may include such as an acryl resin, alkyd resin, vinyl resin, urethane resin, epoxy resin, polyester resin or polyether resin.
• the structural formula represented by formula (1) can be decomposed in the presence of moisture, under an acidic atmosphere, or preferably in an organic solvent, and can be formed, for example, by a reaction of a compound containing carbonyl group with a compound containing hydrazide group and/or a compound containing semicarbazide group.
• the crosslinkable functional group may be introduced, for example, by using a compound containing carbonyl group or hydrazide group which also possesses the crosslinkable functional group.
• Examples of the compound containing carbonyl group include such as diacetone alcohol or 4-hydroxy-2-butanone.
• Examples of the compound containing hydrazide group include such as iminodiacetic acid dihydrazide, adipic acid dihydrazide, carbohydrazide, glutaric acid dihydrazide, azelaic acid dihydrazide, dodecanoyldihydrazide, cyclohexanetricarboxylic acid trihydrazide, tartaric acid dihydrazide or crotonic acid dihydrazide.
• Diacetone acryl amide, acrolein and the like may be mentioned as the compound containing carbonyl group which further possesses a polymerizable double bond as the crosslinkable functional group.
• the resin (A) can be obtained by copolymerizing polymerizable unsaturated monomers each having the structure of the structural formula represented by formula (1) and a crosslinkable functional group, or by addition or condensation reaction of compounds each having the structure of the structural formula represented by formula (1) and a crosslinkable functional group to a polymerization-type resin.
• the resin (A) can be obtained by using a reaction product of a compound containing carbonyl group and hydroxyl group or carboxyl group with a compound containing two or more hydrazide groups and/or semicarbazide groups as at least part of polyhydric alcohol or polybasic acid.
• the resin (A) can be obtained by using a reaction product of a compound containing carbonyl group and hydroxyl group with a compound containing hydrazide group and/or semicarbazide group as a polyhydric alcohol and reacting it with a polyisocyanate.
• the resin (A) can be obtained by adding a reaction product of a compound containing carbonyl group with a compound containing hydrazide group and/or semicarbazide group to an epoxy resin or by adding a compound having amino group or carboxyl group and hydrazide group to an epoxy group and subjecting to dehydrative condensation of a compound having carbonyl group with the hydrazide group.
• the resin (A) can be obtained in a similar manner to the above epoxy resin case using a polyether resin having epoxy groups.
• the crosslinkable functional group to be introduced into the resin (A) at the same time when the structure of the structural formula represented by formula (1) is introduced is not particularly limited, and may be exemplified by a polymerizable double bond, hydroxyl group, carboxyl group, isocyanate group, amino group, thiol group, epoxy group, triazine group, dimide group, silanol group, alkoxysilyl group, methylol group, alkylmethylol group, acetoalkoxy group, carbonyl group, hydrazide group, locked isocyanate group, blocked carboxyl group and blocked hydroxyl group.
• One type or two or more types of these groups may be introduced in the same molecule.
• the resin (A) containing a polymerizable double bond can be by itself cured with crosslinking by oxidative polymerization or irradiation with an active energy beam such as light or electron beam.
• the other crosslinkable functional group is preferably used in combination with a crosslinking agent (B) having a functional group reactive thereto.
• the examples of the crosslinking agent (B) include polyisocyanate compounds, polyepoxy compounds, melamine resins, urea resins, benzoguanamide resins, polyoxy compounds, polycarbonyl compounds, polyhydrazine compounds, polyamine compounds, polysemicarbazide compounds, polydimide compounds, polyacetoacetoxy compounds, polysilanol compounds, polyalkoxysilyl compounds and the like. Two or more of them may be used in combination.
• the curable resin composition of the present invention may contain a coloring pigment, an extender, a thickening agent, a defoaming agent, an organic solvent, water, a plasticizer, a resin other than the above, if necessary.
• the method for curing the curable resin composition of the present invention may be optionally selected depending on the crosslinkable functional group of the resin (A) and the composition of the crosslinking agent (B), and the resin composition can be cured under room temperature, heating, irradiation with an active energy beam and the like.
• the resin composition of the present invention thus cured with crosslinking can be decomposed by bringing it into contact with an aqueous solution of formic acid, acetic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, phosphoric acid or the like, and further with a solution containing an organic solvent, and thereby the cured composition can be removed.
• DENACOL EX-841 an epoxydated polyethylene resin manufactured by Nagase Chemicals Ltd.
• N-methylpyrrolidone an epoxydated polyethylene resin manufactured by Nagase Chemicals Ltd.
• iminodiacetic acid dihydrazide 84 parts by weight
• To the solution was added 177 parts by weight of diacetone acryl amide and 0.3 parts by weight of SUMILIZER BHT (a polymerization inhibitor manufactured by Sumitomo Chemical Co., Ltd.). The mixture was stirred for a long period of time and then stored as it was.
• a phtoinitiator, IRGACURE manufactured by Ciba specialty Chemicals Corp.
• IRGACURE manufactured by Ciba specialty Chemicals Corp.
• Table 1 shows curing conditions, test results of coating properties, and re-dissolving time.
• Example 1 Example 2
• Example 3 Example 4 Added monomer None None i-BMA P-FA2 species Added amount — — 2/1 2/1 (resin/monomer)
• Exposure dose 300 1500 3000 1500 (mmJoule/cm 2 ) Film thickness 20 15 12 18 ( ⁇ m)
• Pencil hardness H H H HB Adhesiveness 100/100 100/100 100/100 Impact 50 ⁇ 50 ⁇ 50 ⁇ 50 ⁇ resistance (1/2 ⁇ ,1 kg)
• the concentration of solid mass of the adduct solution was about 60%. A 200 parts by weight portion of the solution was heated to 80° C and, after the addition of one drop of dibutyltin dilaurate, 37 parts by weight of tolylene diisocyanate (TDI) was added dropwise over a period of one hour, followed by the maintenance at that temperature for further 4 hours. The absence of isocyanate group was confirmed on IR measurement.
• TDI tolylene diisocyanate
• the curable composition of the present invention can be easily decomposed by an aqueous solution of formic acid or the like or the solution additionally containing an organic solvent, and therefore serves an excellent effect that it is easy to recycle the materials to which the composition are attached.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Related Child Applications (1)

Publications (1)

Family

ID=26587406

Family Applications (2)

Family Applications After (1)

Country Status (6)

Cited By (1)

Family Cites Families (13)

• 2001
  • 2001-03-08 SG SG200101437A patent/SG100633A1/en unknown
  • 2001-03-12 CN CNB011094389A patent/CN1185314C/zh not_active Expired - Fee Related
  • 2001-03-13 KR KR1020010012787A patent/KR20010096601A/ko not_active Application Discontinuation
  • 2001-03-13 GB GB0106142A patent/GB2360286B/en not_active Expired - Fee Related
  • 2001-03-13 US US09/804,293 patent/US20020016413A1/en not_active Abandoned
  • 2001-03-14 DE DE10112279A patent/DE10112279A1/de not_active Withdrawn
• 2003
  • 2003-10-03 US US10/677,366 patent/US7084211B2/en not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events