Dithiocarbonate composition

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

Reexamination Certificate

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C524S547000, C549S030000

Reexamination Certificate

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06372871

ABSTRACT:

TECHNICAL FIELD
The present invention relates to dithiocarbonate compositions which are useful in coatings, adhesives, inks, sealing agents for building use, sealants for semiconductors, and the like.
BACKGROUND ART
A reactive polymer or compound which has functional groups in its molecules has various uses. For example, if a composition containing such a polymer or a compound is used as an active ingredient for a coating, an adhesive, an ink, a sealing agent for building use, a sealant for semiconductors or the like, such physical properties as hardness, strength, adhesion, water resistance, chemical resistance, heat resistance, and the like can be improved by allowing cross-linking reactions to occur under specific conditions after application or printing of the composition.
Japanese Unexamined Patent Application, First Publication No. Hei 5-247027 discloses a homopolymer of 5-(methacryloyl)methyl-1,3-oxathiolane-2-thione (MOT) as a polymer having 5-membered dithiocarbonate groups; however, this publication does not disclose a detailed method of polymerization, values expressing physical properties before and after cross-linking reaction, or usefulness of the polymer.
The “Journal of Polymer Science., Part A: Polymer Chemistry” 33, 1005 (1995), discloses a composition comprising a vinyl copolymer having 5-membered ring dithiocarbonate groups and an amine compound. However, since the 5-membered ring dithiocarbonate groups are highly reactive with the amine compound in this composition, this composition cannot be used as a one-liquid type composition for use in a coating or an adhesive, but this composition must be used as a two-liquid type composition in which mixing is performed immediately before use.
Japanese Unexamined Patent Application, First Publication No. Hei 7-145164 discloses a process for cross-linking a compound having 5-membered ring dithiocarbonate groups and a polymer having functional groups containing active hydrogens. Japanese Unexamined Patent Application, First Publication No. Hei 5-247027 describes a composition comprising a compound having 5-membered ring dithiocarbonate groups and a nucleophile. Japanese Unexamined Patent Application, First Publication No. 7-62190 discloses an aqueous polymer composition comprising a vinyl copolymer containing 5-membered ring dithiocarbonate groups and a compound having two or more amino groups or imino groups; however, a combination with a ketimine derivative, an enamine derivative, or an aldimine derivative is not disclosed. It is difficult to use the compositions described in these publications as a one-liquid type coating or adhesive for the reasons described above.
DISCLOSURE OF INVENTION
The present invention provides a composition comprising a polymer or a compound having at least one 5-membered ring dithiocarbonate group represented by general formula (I):
(wherein, in the formula, R
1
, R
2
, and R
3
are the same or different, each of which denotes hydrogen or a lower alkyl), and a ketimine derivative, an enamine derivative, or an aldimine derivative.
In the descriptions of the general formulae of the present invention, “lower alkyl” means a C1 to C4 straight or branched alkali such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and t-butyl.
Examples of the polymer having at least one 5-membered ring dithiocarbonate group represented by general formula (I) are a vinyl polymer, a polyester resin, an alkyd resin, a polyamide resin, a polyether resin, a polyurethane resin, and a copolymer in which these compounds are chemically bonded to each other. Among these, a vinyl polymer is preferable, and a vinyl copolymer containing a structural unit represented by general formula (II)
(wherein, in the formula, the definitions of R
1
, R
2
, and R
3
are the same as those above, R
4
and R
5
are the same or different, each of which denotes hydrogen, methyl, or ethyl, and n denotes an integer of 1 to 4) is more preferable.
The vinyl copolymer having at least one 5-membered ring dithiocarbonate group contains a structural unit having a 5-membered ring dithiocarbonate group and 1 to 10 types of structural units other than the structural unit having a 5-membered ring dithiocarbonate group.
Examples of the vinyl monomer other than the monomer having a 5-membered ring dithiocarbonate group, which is a material for the vinyl copolymer having at least one 5-membered ring dithiocarbonate group, to be copolymerized with the monomer having a 5-membered ring dithiocarbonate group are (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, monoethyl maleate, monomethyl itaconate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, styrene, vinyltoluene, &agr;-methylstyrene, dimethylstyrene, divinylbenzene, N-methylol(meth)acrylamide, (meth)acrylamide, (meth)acrylonitrile, vinyl acetate, vinyl propionate, vinyl versate, monoethyl maleate, monobutyl maleate, diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, diethyl itaconate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, allyl alcohol, allyl alcohol ester, vinyl chloride, vinylidene chloride, fluoroethylene, and chlorofluoroethylene, butadiene. Among these compounds, acrylic acid or methacrylic acid or a lower alkyl ester such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and t-butyl (meth)acrylate can be preferably used. Alternatively, a coplymer of a vinyl monomer and a non-vinyl monomer can be used. Such a copolymer can be produced in accordance with a method for producing a vinyl-modified epoxy resin (Japanese Unexamined Patent Application, First Publication No. Sho 54-30249), a vinyl-modified polyester resin (Japanese Unexamined Patent Application, First Publication No. Hei 1-129072), a vinyl-modified alkyd resin, a vinyl-modified urethane resin (Japanese Unexamined Patent Application, First Publication No. Hei 1-301761), or the like.
In the polymer having at least one 5-membered ring dithiocarbonate group, the content of the structural unit having the 5-membered ring dithiocarbonate group (based on monomer) is preferably 0.2 to 90 mol %.
The molecular weight of the polymer having at least one 5-membered ring dithiocarbonate group is not particularly limited; however, when the polymer is used for a solvent-based coating, one having a weight-average molecular weight of 1,000 to 400,000 can be used, and particularly one having a weight-average molecular weight of 5,000 to 200,000 can be preferably used.
Processes for producing the polymer having at least one 5-membered ring dithiocarbonate group will be explained in the following.
The polymer having at least one 5-membered ring dithiocarbonate group can be obtained by conducting polymerization/polycondensation with a corresponding monomer according to a known method. The monomer having at least one 5-membered ring dithiocarbonate group can be obtained by allowing an oxirane compound and carbon disulfide to react in the presence of alkali halide in accordance with, for example, a known method (Japanese Unexamined Patent Application, First Publication No. Hei 5-257027 or the Journal of Organic Chemistry (J. Org. Chem.), 60, 473 (1995)).
(In the formula, the definitions of R
1
, R
2
, R
3
, R
4
, R
5
, and n are the same as those above.)
Alternatively, the polymer having at least one 5-membered ring dithiocarbonate group can also be produced by obtaining a polymer having a functional group (such as a carboxyl group, a hydroxyl group, or an amino group) in advance, and then allowing a bonding reaction to occur with a 5-membered ring dithiocarbonate compound so that it becomes pendent from the polymer.
Examples o

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