Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2000-02-17
2001-07-03
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S308000, C525S044000, C525S061000, C525S309000, C525S327700, C525S330100
Reexamination Certificate
active
06255444
ABSTRACT:
FIELD OF TECHNOLOGY
This invention relates to aromatic ester (meth)acrylate dendrimers of highly branched structure and curable resin compositions containing said dendrimers as essential component.
BACKGROUND TECHNOLOGY
Curable resin compositions are generally used in coatings, adhesives, and molding materials because of their thermal and mechanical properties. These curable resins are mainly composed of oligomers and monomers and their concrete examples are epoxy acrylates, urethane acrylates, ester acrylates, and unsaturated polyesters. Of these compounds, particularly the oligomeric components exert a great influence on the properties of the coating films to be formed after curing or those of the molded articles and, in consequence, the properties of the oligomeric components assume great importance for manifestation of good material performance. These compounds generally have a linear molecular structure and tend to increase in voscosity and become highly viscous as their molecular weight and content increase; thus it becomes necessary to use the monomeric component and, in some cases, an organic solvent in order to adjust the viscosity to an optimal level for usage.
The monomers used in this manner, however, have a low density of functional groups per molecule and lower the crosslinking density after curing and, furthermore, the residual monomers remaining unreacted in the coating film after curing degrade the mechanical and thermal properties of the film.
In addition, the use of monomeric components and organic solvents is a disadvantage during work on account of odor and, in particular, the use of organic solvents is not necessarily a desirable method for controlling the viscosity because of a growing tendency to avoid it from the standpoint of reducing the release of volatile components.
The use of liquid polyfunctional monomers is another approach to solve the aforementioned problems, but the effect which the monomers of this type produce for lowering the viscosity is no more pronounced than that of monomeric components and organic solvents and, furthermore, the polyfunctionality tends to cause the coating film to undergo large shrinkage after curing and has made it difficult to obtain satisfactory results in respect to the properties of coated films, particularly long-term reliability at high temperature and high humidity.
The present inventors have conducted extensive studies to solve such long outstanding problems, come across aromatic ester (meth)acrylate dendrimers which have a highly branched molecular chain containing terminal (meth)acrylate groups, found that the use of such dendrimers gives curable resin compositions which form cured films of excellent heat and moisture resistance, and completed this invention.
Accordingly, an object of this invention is to solve the aforementioned problems and provide novel aromatic ester (meth)acrylate dendrimers which are low in viscosity, highly curable, and capable of forming cured films of excellent heat and moisture resistance and curable resin compositions containing said dendrimers as essential component.
DISCLOSURE OF THE INVENTION
Thus, this invention relates to an aromatic ester (meth)acrylate dendrimer represented by the following general formula (1)
(in which X is a core-forming aromatic residue of an aromatic compound of 6 to 20 carbon atoms, Y is an organic group of 6 to 20 carbon atoms containing (meth)acrylic group, Z is direct linkage or an aromatic residue of 6 to 20 carbon atoms, m is the number of repeating units from 1 to 10, and n is an integer from 3 to 6).
This invention further relates to a curable resin composition containing the aforementioned aromatic ester (meth)acrylate dendrimer and a polymerization initiator as essential components and to the film obtained by applying the curable resin composition to the substrate.
In an aromatic ester (meth)acrylate dendrimer of this invention, the core X is the aromatic residue originating from the reactant polycarboxylic acid represented by the following general formula
X(COOH)
n
(in which X and n are as defined above) or its derivative such as acid anhydride and acid halide and it preferably comes from aromatic compounds containing the following nucleus
(in which A is a divalent group or direct linakge). Groups preferable as the linking group A are —O—, —S—, —SO
2
—, —CO—, and direct linkage.
In these compounds, the integer n indicating the number of carboxyl groups (including the groups derived from the carboxyl group such as acid halide group and the same holds true hereinafter) in the molecule is preferably 3 to 6. Where n is 2, the molecular chain extends only in two directions with a low degree of branching and the resulting compound is not much different in structure from linear compounds and, undesirably, the special feature which constitutes the object of this invention cannot be manifested. Where n exceeds 6, branched molecular chains tend to become crowded together and, also undesirably, the degree of branching does not increase under the influence of steric hindrance.
Examples of such polycarboxylic acids are 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-(diphenyl ether)tetracarboxylic acid, 3,3′,4,4′-(diphenyl sulfone)tetracarboxylic acid, 2,3′,3′,4′-benzophenonetetracarboxylic acid, 2,3′,3′,4′-biphenyltetracarboxylic acid, 2,3′,3′,4′-(diphenyl ether)tetracarboxylic acid, 2,3′,3′,4′-(diphenyl sulfone)tetracarboxylic acid, 2,2′-bis(3,4-dicarboxyphenoxyphenyl) sulfone, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, pyromellitic acid, mellitic acid, and their derivatives.
In an aromatic ester (meth)acrylate dendrimer of this invention, the highly branched portions are formed by the aromatic residue originating from the reactant aromatic compound containing one hydroxyl group and two carboxylic groups or groups derivative therefrom represented by the following general formula
(in which Z is defined as above) and the group Z is preferably direct linkage or an aromatic residue of 6 to 20 carbon atoms such as shown below.
Examples of such aromatic compounds are 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-(4-hydroxybenzyloxy)isophthalic acid, 5-(4-hydroxybenzylsulfonyl)isophthalic acid, 5-(4-hydroxybenzyl)isophthalic acid, 4-(4-hydroxybenzyloxy)isophthalic acid, 4-(4-hydroxybenzylsulfonyl)isophthalic acid, 4-(4-hydroxybenzyl)isophthalic acid, 2-hydroxyterephthalic acid, 2-(4-hydroxybenzyloxy)terephthalic acid, 2-(4-hydroxybenzylsulfonyl)terephthalic acid, 2-(4-hydroxybenzyl)terephthalic acid and their derivatives.
In the aromatic ester (meth)acrylate dendrimers, the terminal groups are organic groups originating from reactants containing (meth)acrylic group represented by the following general formula
Y-H
(in which Y is defined as above). The H atom here may be replaced with Na or glycidyl group.
These compounds are (meth)acrylic compounds containing hydroxyl groups or groups derivative therefrom necessary for the formation of ester linkage with the carboxylic groups in the aforementioned branch-forming components and the organic group Y is represented by the following general formula
(CH
2
=CR—COO)
n
—Q—O—
(in which Q is a hydrocarbon group of 1 to 17 carbon atoms, R is hydrogen or methyl, and n is an integer from 1 to 5). In this invention, (meth)acrylic refers to acrylic or methacrylic and (meth)acrylate to acrylate or methacrylate.
Concretely, these compounds include pentaerythritol triacrylate, epichlorohydrin(ECH)-modified glycerol triacrylate, ECH-modified 1,6-hexanediol diacrylate, triglycerol diacrylate, ECH-modified ethylene glycol dimethacrylate, glycerol dimethacrylate, glycerol acrylate/methacrylate, ECH-modified propylene glycol diacrylate, ECH-modified trimethylolpropane triacrylate, butanediol monoacrylate, ECH-modified butyl acrylate, glycer
Kawasato Hironobu
Teramoto Takero
Yuasa Masatoshi
Asinovsky Olga
Birch & Stewart Kolasch & Birch, LLP
Nippon Steel Chemical Co. Ltd.
Seidleck James J.
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