CA1245785A - Uv curable high tensile strength resin composition - Google Patents
Uv curable high tensile strength resin compositionInfo
- Publication number
- CA1245785A CA1245785A CA000500755A CA500755A CA1245785A CA 1245785 A CA1245785 A CA 1245785A CA 000500755 A CA000500755 A CA 000500755A CA 500755 A CA500755 A CA 500755A CA 1245785 A CA1245785 A CA 1245785A
- Authority
- CA
- Canada
- Prior art keywords
- acrylate
- composition according
- polyester
- composition
- aromatic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Abstract
ABSTRACT OF THE INVENTION
Disclosed is a resin composition which comprises a mixture of a polyester, an acrylate urethane, in about stoichiometric proportion with the polyester up to about 10% excess polyester over stoichiometric, and a liquid acrylate reactive diluent sufficient to give the resin composition the viscosity of less than 5,000 centipoise.
The polyester resin is the reaction product of a poly-hydroxy compound having at least three hydroxyl groups, and an aromatic compound that is at least difunctional in acid, anhydride, or ester groups, where the proportion of the polyhydroxy compound to the aromatic compound is such that the polyester has about 150 to about 250 mole % excess hydroxyl groups. The acrylate urethane compound is the reaction product of a hydroxy acrylate and an isocyanate having at least two isocyanate groups, where the hydroxy acrylate is equimolar (when a diisocyanate and a hydroxy acrylate having a single hydroxyl group are used) with the isocyanate ? 10 mole %. Also disclosed is a method of making the resin composition.
Disclosed is a resin composition which comprises a mixture of a polyester, an acrylate urethane, in about stoichiometric proportion with the polyester up to about 10% excess polyester over stoichiometric, and a liquid acrylate reactive diluent sufficient to give the resin composition the viscosity of less than 5,000 centipoise.
The polyester resin is the reaction product of a poly-hydroxy compound having at least three hydroxyl groups, and an aromatic compound that is at least difunctional in acid, anhydride, or ester groups, where the proportion of the polyhydroxy compound to the aromatic compound is such that the polyester has about 150 to about 250 mole % excess hydroxyl groups. The acrylate urethane compound is the reaction product of a hydroxy acrylate and an isocyanate having at least two isocyanate groups, where the hydroxy acrylate is equimolar (when a diisocyanate and a hydroxy acrylate having a single hydroxyl group are used) with the isocyanate ? 10 mole %. Also disclosed is a method of making the resin composition.
Description
57~5 l 52,325 W CURA~LE HIGH TENSILE STRENGTH
RESIN COMPOSITION
BAC~GROUND OF THE INVENTION
Amorphous metal strip continuously wound into toroidal cores for use in distribution transformers dramat-ically reduces the magnetic loss compared to orientated steel coils. However, the amorphous metal strip wound cores are very frayile and are not self-supporting, so an external support system is required to protect the cores against mechanical ~orces during handling, winding, and assembly operations. This can be accomplished by coating or encapsulating the cores with a suitable resin. Resins for use in this application must have a very high tensile strength. It is also desirable that they cure rapidly without the evolution of polluting solvents.
SU~MARY OF THE INVENTION
We have discovered a high tensile strength UV
curable resin composition which is ideally suited for use in coating and encapsulating amorphous metal strip cores.
The resin compositions of this invention, without the addition of any filler, have tensile strengths as high as 7200 psi at room temperature and 850 psi at 100C. When a filler is added, of course, the tensile strength of the resulting filled resin is increased. In addition, the filled resin compositions of this invention exhibit ex-tremely good dimensional stability, typically only 7%
elongation at room temperature and 9% elongation at 100~.
'7~j5
RESIN COMPOSITION
BAC~GROUND OF THE INVENTION
Amorphous metal strip continuously wound into toroidal cores for use in distribution transformers dramat-ically reduces the magnetic loss compared to orientated steel coils. However, the amorphous metal strip wound cores are very frayile and are not self-supporting, so an external support system is required to protect the cores against mechanical ~orces during handling, winding, and assembly operations. This can be accomplished by coating or encapsulating the cores with a suitable resin. Resins for use in this application must have a very high tensile strength. It is also desirable that they cure rapidly without the evolution of polluting solvents.
SU~MARY OF THE INVENTION
We have discovered a high tensile strength UV
curable resin composition which is ideally suited for use in coating and encapsulating amorphous metal strip cores.
The resin compositions of this invention, without the addition of any filler, have tensile strengths as high as 7200 psi at room temperature and 850 psi at 100C. When a filler is added, of course, the tensile strength of the resulting filled resin is increased. In addition, the filled resin compositions of this invention exhibit ex-tremely good dimensional stability, typically only 7%
elongation at room temperature and 9% elongation at 100~.
'7~j5
2 52,325 Other advantages of the resin compositions of this invention are that they can be cured very fast, usually in only a few seconds, without the evolution of any solvent. Moreover, coatings as thick as 20 mils or more can be formed from these resin compositions.
DE~CRI~TION OF THE INVENTION
In the first step of the process of this inven-tion, a polyester is prepared by reacting a polyhydroxy compound with an aromatic di- or polyfunctional acid, anhydride, or ester. The polyhydroxy compound is a com-pound ~ ~ contains three or more hydroxyl groups~such as trimethylol propane, tris (2-hydroxyethyl) isocyanurate (THEIC), tris (2-hydroxyethyl) cyanurate, glycerol, tri-methylol ethane, pentaerythritol, trimethylol propane, or erythritol. The preferred polyhydroxy compound is THEIC as that gives a better tensile strength and toughness.
The aromatic di- or polyfunctio~ l~ acid, anhy-dride, or ester is an aromatic compound ~ has two or more acid, anhydrlde, or ester groups, or mixtures of these groups. Difunctional compounds are preferred as there is less chance of a resin composition gelling with a difunc-tional compound. Esters are preferred for a smoother reaction, but compounds having acid groups are less expen-sive. Suitable compounds include terephthalic acid, isophthalic acid, trimellitic acid, trimellitic anhydride
DE~CRI~TION OF THE INVENTION
In the first step of the process of this inven-tion, a polyester is prepared by reacting a polyhydroxy compound with an aromatic di- or polyfunctional acid, anhydride, or ester. The polyhydroxy compound is a com-pound ~ ~ contains three or more hydroxyl groups~such as trimethylol propane, tris (2-hydroxyethyl) isocyanurate (THEIC), tris (2-hydroxyethyl) cyanurate, glycerol, tri-methylol ethane, pentaerythritol, trimethylol propane, or erythritol. The preferred polyhydroxy compound is THEIC as that gives a better tensile strength and toughness.
The aromatic di- or polyfunctio~ l~ acid, anhy-dride, or ester is an aromatic compound ~ has two or more acid, anhydrlde, or ester groups, or mixtures of these groups. Difunctional compounds are preferred as there is less chance of a resin composition gelling with a difunc-tional compound. Esters are preferred for a smoother reaction, but compounds having acid groups are less expen-sive. Suitable compounds include terephthalic acid, isophthalic acid, trimellitic acid, trimellitic anhydride
3,3',4,4'-benzophenone tetracarboxylic dianhydride, pyro-mellitic dianhydride, polyazelaic polyanhydride, pyro-mellitic tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, and alkyl (methyl, ethyl, propyl, etc.) esters of these acids. The preferred aromatic compound is terephthalic acid as it gives better tensile strength.
The polyester reaction product of the polyhydroxy compound and the aromatic compound must have excess hydroxy groups in order to react with the acrylate urethane com-pound, which is also part of the resin composition. If insufficient hydroxyl groups are present on the polyester, 5~
3 52,325 the resin product will have poor tensile strength, and if too ma~y hydroxyl groups are present on the polyester, the resin product will have poor shelf life. If less than 150 mole % excess hydroxyl groups are present, cure is slow, and if more than 250 mole % excess hydroxyl groups are present, unreactive polyhydroxy compound will be present and toughness and tensile strength will be lower. If about 200 mole % excess hydroxyl groups are present ~n the polyester, the resin product will have the maximum tensile strength. The proportions of polyhydroxy compound to aromatic compound are adjusted to give a mole % of excess hydroxyl groups within this range. The reaction of the polyhydroxy compound with the aromatic compound proceeds without the presence of a solvent, but a suitable amount 15 (about 0.05 to about 0.50 parts per lOO parts resin (phr)) of an esterification catalyst is needed. Any esterifica~
?;~'"' ~
tion catalyst~ such as dibutyl tin oxide, tetraisopropyL
titanate, dihydroxy butyl tln chloride, triphenyl tin chloride, or triphenyL tin acetate can be used. Dibutyl tin oxide is preferred as it is an inexpensive, readily avaiLable, and works well. The composition of the poly-hydroxy compound and the aromatic compound is mixed thor-oughly and is heated in 15C increments over about a one hour period to a temperature of about 210 to about 250C, or until no further condensate is emitted.
The reaction of the polyhydroxy compound with the aromatic compound produces an ester oligomer having excess hydroxyl groups:
O O
1~ 11 R OHl + COOH-R2-C~GH -~ HO-~l- C R2 ll 2 OH OH OH
In the next step in the process of this in~en-tion, an acrylate urethane is produced by the reaction of a hydroxy acrylate with an isocyanate. The hydroxy acrylate is a compound having at least one hydroxyl group and at least one acrylate group. Preferably~ the hydroxy acrylate y~
~ 52,325 includes only a single hydroxyl group because polyhydroxy groups will form a high molecular weight polymer with isocyanate instead of the adduct of hyd:roxyethyl acrylate and isocyanate. Also, the hydroxy acrylate preferably includes only a single acrylate group because the poly-acrylate group will increase the undesi:red properties such as brittleness and high shrinkage. Suitable hydroxy acrylates include hydroxyethyl acrylate, hydroxyethyl-~-carboxyethyl acrylate, and 3-hydroxyethyl acrylate. Hydrox-yethyl acrylate is preferred as it is readily available and produces a tougher product. Aromatic hydroxy acrylates are preferred for thermal stability and toughness; however, they are not commercially available at this time.
The isocyanate compound used in preparing the acrylate urethane must have two or more isocyanate groups.
Preferably, the isocyanate compound ls an aromatic compound as they produce tougher resln products. Sui~able isocyan-ate compounds include meta-phenylene diisocyana~e, tol-uylene diisocyanate, hexamethylene diisocyanate, meta-xylyene diisocyanate, 4,41-diisocyanato diphenyl sulfone,
The polyester reaction product of the polyhydroxy compound and the aromatic compound must have excess hydroxy groups in order to react with the acrylate urethane com-pound, which is also part of the resin composition. If insufficient hydroxyl groups are present on the polyester, 5~
3 52,325 the resin product will have poor tensile strength, and if too ma~y hydroxyl groups are present on the polyester, the resin product will have poor shelf life. If less than 150 mole % excess hydroxyl groups are present, cure is slow, and if more than 250 mole % excess hydroxyl groups are present, unreactive polyhydroxy compound will be present and toughness and tensile strength will be lower. If about 200 mole % excess hydroxyl groups are present ~n the polyester, the resin product will have the maximum tensile strength. The proportions of polyhydroxy compound to aromatic compound are adjusted to give a mole % of excess hydroxyl groups within this range. The reaction of the polyhydroxy compound with the aromatic compound proceeds without the presence of a solvent, but a suitable amount 15 (about 0.05 to about 0.50 parts per lOO parts resin (phr)) of an esterification catalyst is needed. Any esterifica~
?;~'"' ~
tion catalyst~ such as dibutyl tin oxide, tetraisopropyL
titanate, dihydroxy butyl tln chloride, triphenyl tin chloride, or triphenyL tin acetate can be used. Dibutyl tin oxide is preferred as it is an inexpensive, readily avaiLable, and works well. The composition of the poly-hydroxy compound and the aromatic compound is mixed thor-oughly and is heated in 15C increments over about a one hour period to a temperature of about 210 to about 250C, or until no further condensate is emitted.
The reaction of the polyhydroxy compound with the aromatic compound produces an ester oligomer having excess hydroxyl groups:
O O
1~ 11 R OHl + COOH-R2-C~GH -~ HO-~l- C R2 ll 2 OH OH OH
In the next step in the process of this in~en-tion, an acrylate urethane is produced by the reaction of a hydroxy acrylate with an isocyanate. The hydroxy acrylate is a compound having at least one hydroxyl group and at least one acrylate group. Preferably~ the hydroxy acrylate y~
~ 52,325 includes only a single hydroxyl group because polyhydroxy groups will form a high molecular weight polymer with isocyanate instead of the adduct of hyd:roxyethyl acrylate and isocyanate. Also, the hydroxy acrylate preferably includes only a single acrylate group because the poly-acrylate group will increase the undesi:red properties such as brittleness and high shrinkage. Suitable hydroxy acrylates include hydroxyethyl acrylate, hydroxyethyl-~-carboxyethyl acrylate, and 3-hydroxyethyl acrylate. Hydrox-yethyl acrylate is preferred as it is readily available and produces a tougher product. Aromatic hydroxy acrylates are preferred for thermal stability and toughness; however, they are not commercially available at this time.
The isocyanate compound used in preparing the acrylate urethane must have two or more isocyanate groups.
Preferably, the isocyanate compound ls an aromatic compound as they produce tougher resln products. Sui~able isocyan-ate compounds include meta-phenylene diisocyana~e, tol-uylene diisocyanate, hexamethylene diisocyanate, meta-xylyene diisocyanate, 4,41-diisocyanato diphenyl sulfone,
4,~'-diisocyanato diphenyl ether, and 4,4'-diisocyanato diphenyl methane. The preferred isocyanate is toluylene diisocyanate as it is readily available and gives a tougher product.
In reacting the hydroxy acrylate compound with the isocyanate compound, equimolar (if a diisocyanate and a hydroxy acrylate having a single hydroxyl group are used) amounts are used, though either component may be present in up to about 10 mole % excess of equimolar (if a diisocy-anate and a hydroxy acrylate having a single hydroxyl group are used). No solvent or catalyst is required. The mixture of the hydroxy acrylate and the isocyanate compound -reacts exothermically and is preferably cooled to under 70C
during the reaction because a higher reaction temperature will give a premature gellation. After about one hour the reaction is usually complete. The reaction of hydroxy acrylate with the isocyanate compound produces an acrylate urethane, containing one urethane group and one nonreacted isocyanate group.
.. ,~
tJ~
52,325 R3-OH ~ O=C=N-R4-N=C=0 ~ R3-0-C NH-R4-N=C=O
o In the next step of the process of this inven-tion, the polyester is reacted with the acrylate urethane.
These two components are reacted stoichiometrically, although up to about 10 mole % excess polyester may be present. Excess acrylate urethane, however, should not be present as it is toxic in the product. A stoichiometric reaction would typically mean that about 4 moles of acry-late urethane are present for each mole of polyester that is present. Whi1e no solvent is required for this reac-tion, it is necessary to include a reactive diluent to solubilize the polyester and the acrylate urethane. Unlike a solvent, a raactive diluent is reacted into the rasin product and is not volatilized durlng resin cure. The lS reactive diluent is a liquid acrylate which has a vi~cosity of less than 1,000 centipoises (cps). The acrylate prefer-ably has two or more acrylate groups as this gives greater tensile strength in the product. Suitable examples of acrylates which can be used as reactive diluents include tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, diethylaneglycol diacrylate, 1,6-hexanediol diacrylate and neopentyl glycol diacrylate. The preferred reactive diluent is tetraethyl-ene glycol diacrylate because it has a low viscosity and gives a high tensile strength to the product. Sufficient reactive diluent should be used so that the resin compo-sition has a viscosity of less than 5,000 cps. If the resin composition viscosity is greater, the resin composi-tion will not flow readily and will not fill all of the interstices of the substrate. Typically, this means that the reactive diluent constitutes about 20 to about 60 % by weight of the total weight of the resin composi~ion.
If the resin composition is not to be used soon after i~ is prepared~it is desirable to include about 0.005 6 52,325 to about 0.05 % by weight (based on total resin composition weight) of an inhibitor to add to its shelf life. If less inhibitor is used the resin composition may start to gel during storage, and if more is used it may be difficult to gel the composition when it is used. Suitable inhibitors include benzoquinone, methyl-p-benzoquirlone, hydroquinone, h~droquinone monoethyl ether, and 2,3,5,6-tetrachlorobenzo-quinone. The preferred inhibitor is benzoquinone because it is readily available and it works well.
A photoinitiator sensitive to ultraviolet (UV) light is reauired to cure the composition, but the photo-initiator need not be added to the composition until it is read~ to be used. Particularly stable photoinitiators can, however, be mixed into the resin composition when it is stored. ~xamples of suitable photoinitiators include isopropyl ben~oin ether, diethoxy phenyl acetophenone, 2,2-dimethoxy--2-phenyl acetophenone, isobutyL benzoin ether, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one. The preferred photoinitiator is isobutyl benzoin ether because it is inexpensive, it is in easily applied liquid form, and has been found to work very well. Isobutyl benzoin ether is normally not added to the resin composition until the composition is to be applied and cured. Typically about 1 to about 5 phr of the photoinitiator is satisfactory.
The tensile strength of the cured resin composi-tion can be further increased by the addition of up to about 50 % by weight (based on total composition weight) of a filler. The filler should be transparent to ultraviolet light so that it does not absorb the ultraviolet light and prevent the resin composition from curing. Suitable fillers include fibers, roving, mat, or cloth of glass, polyethylene terephthalate, mica, ~uartz, silica, talc, calcium carbonate, and boron. The preferred filler is glass cloth as it has a very high tensile strength and has been found to work well.
When it is desired to use the resin composition, it is applied to a surface and is exposed to ultraviolet s 7 52,325 light. Any type of ultraviolet light is effecti~e alld a cornplete cure will normally occur in only a few seconds by a free radical curing mechanism.
The resin compositions of this inven~ion are primarily intended for use in bonding amorphous metal cores.
In that application, a primer resin is first applied to the core to insure good adhesion of the resin composition to the core. After the primer composition is app].ied, a filler is pressed into the primer coating, then the primer coating is cured. An example of a suitable primer composition can be found in U.S. Patent 4,481,258, which discloses an acrylated epoxy resin. The resin composition of this invention is then applied over the primer coating, filler is pressed into the resin coating, and the resin coating is cured with UV light.
Any number of layers of the resin coating and filler can be applied to build up the total thickness of the coating. It is preferable to post bake the coatings after UV curing to insure that the resin compositions have been comple~ely cured.
This can be accomplished by heating for 2 to 5 hours at abou-t 100 to 150C.
The resin compositions of this invention can also be used as adhesives, encapsulants, or as coatings in other applications.
The following example further illustrates this invention.
EXAMPLE
A polyester resin was made in a three liter four-neck reaction flask equipped with stirrer, thermometer, nitrogen sparge, and downward distillation column. The flask was charged with 218.6 grams of tris (2 hydroxyethyl) isocy-anurate, 69.8 grams of terephthalic acid, and 3.5 grams of deionized water. The reaction mixture was heated to 140C, and 0.8 grams of dibutyl tin oxide was added. The mixture was then reacted at 210 to 250C in 15C increments per hour until 17 ml of water was collected. The temperature was reduced to 120C and the resin ~5~~
8 52,325 was cut witil 517 grams tetraethylene glycol diacrylate (TEGDA).
An acrylate urethane was prepared in a one liter four~neck reaction flask equipped with stirrer, thermome-ter, nitrogen sparge, and water bath for cooling. Theflask was charged ~Jith 194.4 grams 2-hydroxyethyl acrylate and 0.1 grams benzo~uinone. To the mixture was gradually added 291.6 grams toluylene diisocyanate and the reaction mix~ure was kept cooled to a temperature just below 60~C.
After all the toluylene diisocyanate was added, the mixture was reacted at 60 to 70C for one hour. The acrylate urethane was poured under nitrogen into an air-tight tared container.
A resin composition was prepared by mixing 486 grams of the acrylate urethane with the entire amount of the polyester resin described above. The mixture was reacted 120C for one hour and was cut with 621,0 grams TECDA, then poured into a ta~ed container. The viscoslty of the resin composition was in the range of 3,000 to 5,000 cps at 25C. The resin was sensitized by the addition of 4 phr isobutyl benzoin ether sold by Stauffer Chemical Company under a trade designation "V-lO." This composition is identified as composition A.
Identical compositions B, C, and D were prepared in the same manner except that the 60% TEGDA was replaced with 26.7% phenoxyethyl acrylate (PEA) and 33.3% TEGDA, or 60% PEA, or 26.7% TEGDA and 33.3% trimethyl propane tri-acrylate (TMPTA), respectively.
Transformer oil compatibility tests (ASTMD-3455-78) were carried out using pieces of amorphous metal strip2 inches wide by 5 inches long by 0.005 inches thick. The specimens were coated with a primer composition which consisted of 56.70% (by weight) acrylated epoxy, 6.45%
acrylated urethane, 24.10% phenoxy ethyl acrylate, 7.98%
tetra ethylene glycol diacrylate and 3.85% isobutyl benzoin ether. A fiberglass cloth 4 inches by 12 inches was pressed into the primer composition coating and it was t~.S
9 52,325 cured with UV light. Compositions A, B, C, and D were then coated onto other specimens, a similar glass cloth was pressed into these coatings, and they were cured with UV
light. The specimens were all post baked for four hours at 150C. The results of the ASTM test indicated that the cured resin compositions do not contaminate transformer oil.
A 25 pound rectangular amorphous metal coil was encapsulated in the same manner and was then thermally cycled between -35C and 110C, nine times in air and nine times in transformer oil. The coating showed no visible damage after the c~ycling.
In other tests, coatings of the resins were applied to the mold of tensile test specimens (ASTM
0638-77a) until a layer 13 mils thick was obtained. Some of the coatings were post baked for four hours at 130C and sorne were not. The coatinqs were then tested for tensile strencJth and elongation at room temperature and at 100C.
The followincJ table gives the results.
s lQ 52,325 o ~ D j ~ ~ 3~ ~,æO~
D~ ~ ~V~
~ o A¦ 0 8 ~
t I ,~, ~o I o I ~ o ~oo .
~ .
D æ ~ O
a ~ D ;~
. .,i ,,, ;d ~. S 7 ~ .5 11 5~,325 The above table shows that the composition~ that contained tetraethylene glycol diacrylate had superior tensile strength compared to the compositions that instead contained a monofunctional acrylate. Composition D, while it had high tensile strength, shrunk a great deal after curing. This may adversely affect the magnetic properties of a metal substrate, and may make it unsuitable for use in coating magnetic cores.
In reacting the hydroxy acrylate compound with the isocyanate compound, equimolar (if a diisocyanate and a hydroxy acrylate having a single hydroxyl group are used) amounts are used, though either component may be present in up to about 10 mole % excess of equimolar (if a diisocy-anate and a hydroxy acrylate having a single hydroxyl group are used). No solvent or catalyst is required. The mixture of the hydroxy acrylate and the isocyanate compound -reacts exothermically and is preferably cooled to under 70C
during the reaction because a higher reaction temperature will give a premature gellation. After about one hour the reaction is usually complete. The reaction of hydroxy acrylate with the isocyanate compound produces an acrylate urethane, containing one urethane group and one nonreacted isocyanate group.
.. ,~
tJ~
52,325 R3-OH ~ O=C=N-R4-N=C=0 ~ R3-0-C NH-R4-N=C=O
o In the next step of the process of this inven-tion, the polyester is reacted with the acrylate urethane.
These two components are reacted stoichiometrically, although up to about 10 mole % excess polyester may be present. Excess acrylate urethane, however, should not be present as it is toxic in the product. A stoichiometric reaction would typically mean that about 4 moles of acry-late urethane are present for each mole of polyester that is present. Whi1e no solvent is required for this reac-tion, it is necessary to include a reactive diluent to solubilize the polyester and the acrylate urethane. Unlike a solvent, a raactive diluent is reacted into the rasin product and is not volatilized durlng resin cure. The lS reactive diluent is a liquid acrylate which has a vi~cosity of less than 1,000 centipoises (cps). The acrylate prefer-ably has two or more acrylate groups as this gives greater tensile strength in the product. Suitable examples of acrylates which can be used as reactive diluents include tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, diethylaneglycol diacrylate, 1,6-hexanediol diacrylate and neopentyl glycol diacrylate. The preferred reactive diluent is tetraethyl-ene glycol diacrylate because it has a low viscosity and gives a high tensile strength to the product. Sufficient reactive diluent should be used so that the resin compo-sition has a viscosity of less than 5,000 cps. If the resin composition viscosity is greater, the resin composi-tion will not flow readily and will not fill all of the interstices of the substrate. Typically, this means that the reactive diluent constitutes about 20 to about 60 % by weight of the total weight of the resin composi~ion.
If the resin composition is not to be used soon after i~ is prepared~it is desirable to include about 0.005 6 52,325 to about 0.05 % by weight (based on total resin composition weight) of an inhibitor to add to its shelf life. If less inhibitor is used the resin composition may start to gel during storage, and if more is used it may be difficult to gel the composition when it is used. Suitable inhibitors include benzoquinone, methyl-p-benzoquirlone, hydroquinone, h~droquinone monoethyl ether, and 2,3,5,6-tetrachlorobenzo-quinone. The preferred inhibitor is benzoquinone because it is readily available and it works well.
A photoinitiator sensitive to ultraviolet (UV) light is reauired to cure the composition, but the photo-initiator need not be added to the composition until it is read~ to be used. Particularly stable photoinitiators can, however, be mixed into the resin composition when it is stored. ~xamples of suitable photoinitiators include isopropyl ben~oin ether, diethoxy phenyl acetophenone, 2,2-dimethoxy--2-phenyl acetophenone, isobutyL benzoin ether, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one. The preferred photoinitiator is isobutyl benzoin ether because it is inexpensive, it is in easily applied liquid form, and has been found to work very well. Isobutyl benzoin ether is normally not added to the resin composition until the composition is to be applied and cured. Typically about 1 to about 5 phr of the photoinitiator is satisfactory.
The tensile strength of the cured resin composi-tion can be further increased by the addition of up to about 50 % by weight (based on total composition weight) of a filler. The filler should be transparent to ultraviolet light so that it does not absorb the ultraviolet light and prevent the resin composition from curing. Suitable fillers include fibers, roving, mat, or cloth of glass, polyethylene terephthalate, mica, ~uartz, silica, talc, calcium carbonate, and boron. The preferred filler is glass cloth as it has a very high tensile strength and has been found to work well.
When it is desired to use the resin composition, it is applied to a surface and is exposed to ultraviolet s 7 52,325 light. Any type of ultraviolet light is effecti~e alld a cornplete cure will normally occur in only a few seconds by a free radical curing mechanism.
The resin compositions of this inven~ion are primarily intended for use in bonding amorphous metal cores.
In that application, a primer resin is first applied to the core to insure good adhesion of the resin composition to the core. After the primer composition is app].ied, a filler is pressed into the primer coating, then the primer coating is cured. An example of a suitable primer composition can be found in U.S. Patent 4,481,258, which discloses an acrylated epoxy resin. The resin composition of this invention is then applied over the primer coating, filler is pressed into the resin coating, and the resin coating is cured with UV light.
Any number of layers of the resin coating and filler can be applied to build up the total thickness of the coating. It is preferable to post bake the coatings after UV curing to insure that the resin compositions have been comple~ely cured.
This can be accomplished by heating for 2 to 5 hours at abou-t 100 to 150C.
The resin compositions of this invention can also be used as adhesives, encapsulants, or as coatings in other applications.
The following example further illustrates this invention.
EXAMPLE
A polyester resin was made in a three liter four-neck reaction flask equipped with stirrer, thermometer, nitrogen sparge, and downward distillation column. The flask was charged with 218.6 grams of tris (2 hydroxyethyl) isocy-anurate, 69.8 grams of terephthalic acid, and 3.5 grams of deionized water. The reaction mixture was heated to 140C, and 0.8 grams of dibutyl tin oxide was added. The mixture was then reacted at 210 to 250C in 15C increments per hour until 17 ml of water was collected. The temperature was reduced to 120C and the resin ~5~~
8 52,325 was cut witil 517 grams tetraethylene glycol diacrylate (TEGDA).
An acrylate urethane was prepared in a one liter four~neck reaction flask equipped with stirrer, thermome-ter, nitrogen sparge, and water bath for cooling. Theflask was charged ~Jith 194.4 grams 2-hydroxyethyl acrylate and 0.1 grams benzo~uinone. To the mixture was gradually added 291.6 grams toluylene diisocyanate and the reaction mix~ure was kept cooled to a temperature just below 60~C.
After all the toluylene diisocyanate was added, the mixture was reacted at 60 to 70C for one hour. The acrylate urethane was poured under nitrogen into an air-tight tared container.
A resin composition was prepared by mixing 486 grams of the acrylate urethane with the entire amount of the polyester resin described above. The mixture was reacted 120C for one hour and was cut with 621,0 grams TECDA, then poured into a ta~ed container. The viscoslty of the resin composition was in the range of 3,000 to 5,000 cps at 25C. The resin was sensitized by the addition of 4 phr isobutyl benzoin ether sold by Stauffer Chemical Company under a trade designation "V-lO." This composition is identified as composition A.
Identical compositions B, C, and D were prepared in the same manner except that the 60% TEGDA was replaced with 26.7% phenoxyethyl acrylate (PEA) and 33.3% TEGDA, or 60% PEA, or 26.7% TEGDA and 33.3% trimethyl propane tri-acrylate (TMPTA), respectively.
Transformer oil compatibility tests (ASTMD-3455-78) were carried out using pieces of amorphous metal strip2 inches wide by 5 inches long by 0.005 inches thick. The specimens were coated with a primer composition which consisted of 56.70% (by weight) acrylated epoxy, 6.45%
acrylated urethane, 24.10% phenoxy ethyl acrylate, 7.98%
tetra ethylene glycol diacrylate and 3.85% isobutyl benzoin ether. A fiberglass cloth 4 inches by 12 inches was pressed into the primer composition coating and it was t~.S
9 52,325 cured with UV light. Compositions A, B, C, and D were then coated onto other specimens, a similar glass cloth was pressed into these coatings, and they were cured with UV
light. The specimens were all post baked for four hours at 150C. The results of the ASTM test indicated that the cured resin compositions do not contaminate transformer oil.
A 25 pound rectangular amorphous metal coil was encapsulated in the same manner and was then thermally cycled between -35C and 110C, nine times in air and nine times in transformer oil. The coating showed no visible damage after the c~ycling.
In other tests, coatings of the resins were applied to the mold of tensile test specimens (ASTM
0638-77a) until a layer 13 mils thick was obtained. Some of the coatings were post baked for four hours at 130C and sorne were not. The coatinqs were then tested for tensile strencJth and elongation at room temperature and at 100C.
The followincJ table gives the results.
s lQ 52,325 o ~ D j ~ ~ 3~ ~,æO~
D~ ~ ~V~
~ o A¦ 0 8 ~
t I ,~, ~o I o I ~ o ~oo .
~ .
D æ ~ O
a ~ D ;~
. .,i ,,, ;d ~. S 7 ~ .5 11 5~,325 The above table shows that the composition~ that contained tetraethylene glycol diacrylate had superior tensile strength compared to the compositions that instead contained a monofunctional acrylate. Composition D, while it had high tensile strength, shrunk a great deal after curing. This may adversely affect the magnetic properties of a metal substrate, and may make it unsuitable for use in coating magnetic cores.
Claims (32)
1. A resin composition containing no non-reactive solvent comprising (A) a polyester that comprises the reaction product of (1) polyhydroxy compound having at least three hydroxyl groups, and (2) aromatic compound that is at least difunc-tional in a group selected from acid, anhydride, ester, and mixtures thereof, where the proportion of said polyhydroxy compound to said aromatic compound is selected so that said polyester has about 150 to about 250 mole % excess hydroxyl groups;
(B) an acrylate urethane in about stoichiometric proportion with said polyester up to about 10%
excess polyester over stoichiometric, where said acrylate urethane comprises the reaction product of (1) hydroxy acrylate having a single hydroxyl group; and (2) diisocyanate, said hydroxy acrylate being equimolar ? 10 mole % with said diisocyante;
and (C) liquid acrylate reactive diluent sufficient to give said resin composition a viscosity of less than 5000 cps.
(B) an acrylate urethane in about stoichiometric proportion with said polyester up to about 10%
excess polyester over stoichiometric, where said acrylate urethane comprises the reaction product of (1) hydroxy acrylate having a single hydroxyl group; and (2) diisocyanate, said hydroxy acrylate being equimolar ? 10 mole % with said diisocyante;
and (C) liquid acrylate reactive diluent sufficient to give said resin composition a viscosity of less than 5000 cps.
2. A composition according to Claim 1 which includes about 0.005 to about 0.5% by weight of an inhibi-tor.
3. A composition according to Claim 2 wherein said inhibitor is benzoquinone.
4. A composition according to Claim 1 wherein said polyhydroxy compound is tris (2-hydroxyethyl) isocy-anate.
5. A composition according to Claim 1 wherein said aromatic compound is difunctional.
6. A composition according to Claim 5 wherein said aromatic compound is terephthalic acid.
7. A composition according to Claim 1 wherein said aromatic compound has ester functionality.
8. A composition according to Claim 1 wherein said hydroxy acrylate is hydroxyethyl acrylate.
9. A composition according to Claim 1 wherein said isocyanate is aromatic.
10. A composition according to Claim 9 wherein said isocyanate is toluylene diisocyanate.
11. A composition according to Claim 1 wherein the amount of said reactive diluent is about 20 to about 60% by weight, based on total composition weight.
12. A composition according to Claim 1 wherein said reactive diluent has at least two acrylate groups.
13. A composition according to Claim 1 wherein said reactive diluent has a viscosity of less than 1000 cps.
14. A composition according to Claim 13 wherein said reactive diluent is tetraethylene glycol diacrylate.
15. A composition according to Claim 1 which includes up to about 50% by weight, based on total composi-tion weight of a filler that is transparent to UV light.
16. A composition according to Claim 15 wherein said filler is glass.
17. A composition according to Claim 1 which includes about 1 to about 5 phr of a UV photoinitiator.
18. A composition according to Claim 17 wherein said photoinitiator is isobutyl benzoin ether.
19. A coating comprising a cured composition according to Claim 17.
20. A composition containing no non-reactive solvent comprising (A) a polyester that comprises the reaction product of (1) tris (2-hydroxy ethyl) isocyanurate; and (2) an aromatic compound that is difunctional in a group selected from acid, anhydride, ester, and mixtures thereof, where the proportion of said polyhydroxy compound to said aromatic compound is selected so that said polyester has about 150 to about 250 mole % excess hydroxyl groups;
(B) an acrylate urethane in about stoichiometric proportion with said polyester up to about 10%
excess polyester over stoichiometric, where said acrylate urethane comprises the reaction product of (1) hydroxy acrylate having a single hydroxyl group and a single acrylate group; and (2) an aromatic diisocyanate, said hydroxy acrylate being equimolar ? 10 mole % with said isocyanate;
(C) about 20 to about 60% by weight, based on total composition weight, of a liquid acrylate re-active diluent having at least two acrylate groups and a viscosity of less than 1000 cps;
(D) about 0.005 to about 0.5% by weight of an inhibitor;
(E) about 1 to about 5 phr of a UV photoinitiator;
and (F) up to about 50% by weight, based on total composition weight, of a filler that is transparent to UV light.
(B) an acrylate urethane in about stoichiometric proportion with said polyester up to about 10%
excess polyester over stoichiometric, where said acrylate urethane comprises the reaction product of (1) hydroxy acrylate having a single hydroxyl group and a single acrylate group; and (2) an aromatic diisocyanate, said hydroxy acrylate being equimolar ? 10 mole % with said isocyanate;
(C) about 20 to about 60% by weight, based on total composition weight, of a liquid acrylate re-active diluent having at least two acrylate groups and a viscosity of less than 1000 cps;
(D) about 0.005 to about 0.5% by weight of an inhibitor;
(E) about 1 to about 5 phr of a UV photoinitiator;
and (F) up to about 50% by weight, based on total composition weight, of a filler that is transparent to UV light.
21. A method of making a resin composition con-taining no non-reactive solvent comprising (1) preparing a first composition which comprises (a) polyhydroxy compound having at least three hydroxyl groups;
(b) aromatic compound that is at least difunctional in a group selected from acid, anhydride, ester, and mixtures thereof, where the proportion of said polyhydroxy compound to said aromatic compound is selected so that the hydroxyl functionality is about 150 to about 250 mole % in excess of stoichiometic; and (c) sufficient amount of an esterification catalyst;
(2) heating said first composition to produce a polyester;
(3) preparing a second composition which comprises (a) hydroxy acrylate having a single hydroxyl group; and (b) diisocyanate, said hydroxy acrylate being equimolar ? 10 mole % with said diisocy-anate;
(4) allowing said second composition to exotherm to produce an acrylate urethane;
(5) preparing a resin composition which comprises (a) said polyester;
(b) said acrylate urethane in an amount from about stoichiometric with said polyester to about 10% excess of said polyester over stoichiometric;
(c) liquid acrylate reactive diluent suffi-cient to give said resin composition a viscosity of less than 5000 cps.
(b) aromatic compound that is at least difunctional in a group selected from acid, anhydride, ester, and mixtures thereof, where the proportion of said polyhydroxy compound to said aromatic compound is selected so that the hydroxyl functionality is about 150 to about 250 mole % in excess of stoichiometic; and (c) sufficient amount of an esterification catalyst;
(2) heating said first composition to produce a polyester;
(3) preparing a second composition which comprises (a) hydroxy acrylate having a single hydroxyl group; and (b) diisocyanate, said hydroxy acrylate being equimolar ? 10 mole % with said diisocy-anate;
(4) allowing said second composition to exotherm to produce an acrylate urethane;
(5) preparing a resin composition which comprises (a) said polyester;
(b) said acrylate urethane in an amount from about stoichiometric with said polyester to about 10% excess of said polyester over stoichiometric;
(c) liquid acrylate reactive diluent suffi-cient to give said resin composition a viscosity of less than 5000 cps.
22. A transformer coil coated with a resin composition containing no non-reactive solvent which comprises:
(A) a polyester that comprises the reaction product of (1) polyhydroxy compound having at least three hydroxyl groups, and (2) aromatic compound that is at least difunctional in a group selected from acid, anhydride, ester, and mixtures thereof, where the proportion of said polyhydroxy compound to said aromatic compound is selected so that said poly-ester has about 150 to about 250 mole %
excess hydroxyl groups;
(B) an acrylate urethane in about stoichiometric proportion with said polyester up to about 10%
excess polyester over stoichiometric, where said acrylate urethane comprises the reaction product of (1) hydroxy acrylate having a single hydroxyl group; and (2) diisocyanate said hydroxy acrylate being equimolar ? 10 mole % with said diisocy-anate; and (C) liquid acrylate reactive diluent sufficient to give said resin composition a viscosity of less than 5000 cps.
(A) a polyester that comprises the reaction product of (1) polyhydroxy compound having at least three hydroxyl groups, and (2) aromatic compound that is at least difunctional in a group selected from acid, anhydride, ester, and mixtures thereof, where the proportion of said polyhydroxy compound to said aromatic compound is selected so that said poly-ester has about 150 to about 250 mole %
excess hydroxyl groups;
(B) an acrylate urethane in about stoichiometric proportion with said polyester up to about 10%
excess polyester over stoichiometric, where said acrylate urethane comprises the reaction product of (1) hydroxy acrylate having a single hydroxyl group; and (2) diisocyanate said hydroxy acrylate being equimolar ? 10 mole % with said diisocy-anate; and (C) liquid acrylate reactive diluent sufficient to give said resin composition a viscosity of less than 5000 cps.
23. A composition according to Claim 1 wherein said polyester has about 200 mole % excess hydroxyl groups.
24 A composition according to Claim 1 wherein said hydroxy acrylate is selected from the group consisting of hydroxyethyl acrylate, hydroxethyl-.beta.-carboxyethyl acrylate, 3-hydroxyethyl acrylate, and mixtures thereof.
25. A composition according to Claim 1 wherein said isocyanate is selected from the group consisting of metaphenylene diisocyanate, toluylene diisocyanate, hexamethyl-ene diisocyanate, meta-xylene diisocyanate, 4,4'-diisocyanato diphenyl sulfone, 4,4'-diisocyanato diphenyl ether, 4,4'-diisocyanato diphenyl methane, and mixtures thereof.
26. A composition according to Claim 1 wherein said polyhydroxy compound is selected from the group consisting of trimethylol propane, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) cyanurate, glycerol, trimethylol ethane, pentaerythritol, trimethylol propane, erythritol, and mixtures thereof.
27. A composition according to Claim 1 wherein said aromatic compound is selected from the group consisting of terephthalic acid, isophthalic acid, trimellitic acid, tri-mellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, polyazelaic polyanhy-dride, pyromellitic tetracarboxylic acid, 3,3',4,4'-benzophe-none tetracarboxylic acid, and esters and mixtures thereof.
28, A composition according to Claim 1 wherein said reactive diluent is selected from the group consisting of tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, diethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and mixtures thereof.
29. A composition according to Claim 2 wherein said inhibitor is selected from the group consisting of benzoquinone methyl-p-benzoquinone, hydroquinone, hydro-quinone monoethyl ether, 2,3,5,6-tetrachlorobenzoquinone, and mixtures thereof.
30, A composition according to Claim 18 wherein said photoinitiator is selected from the group consisting of isopropyl benzoin ether, diethoxy phenyl acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, isobutyl benzoin ether, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and mixtures thereof.
31, A resin made from a composition according to Claim 1, having the structure where PH is the residue of said polyhydroxy compound, A
is the residue of said aromatic compound, HA is the residue of said hydroxy acrylate, where said hydroxy acrylate has a single hydroxyl group, I is the residue of said isocyanate, where said isocyanate is a diisocyanate, p is one less than the number of hydroxyl groups on said polyhydroxy compound, and q is the functionality of said aromatic compound.
is the residue of said aromatic compound, HA is the residue of said hydroxy acrylate, where said hydroxy acrylate has a single hydroxyl group, I is the residue of said isocyanate, where said isocyanate is a diisocyanate, p is one less than the number of hydroxyl groups on said polyhydroxy compound, and q is the functionality of said aromatic compound.
32. A resin according to Claim 31 wherein said hydroxy acrylate is hydroxyethyl acrylate, said isocyanate is toluylene diisocyanate, said polyhydroxy compound is tris (2-hydroxyethyl) isocyanurate, and said aromatic compound is terephthalic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US699,373 | 1985-02-07 | ||
| US06/699,373 US4618632A (en) | 1985-02-07 | 1985-02-07 | UV curable high tensile strength resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1245785A true CA1245785A (en) | 1988-11-29 |
Family
ID=24809038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000500755A Expired CA1245785A (en) | 1985-02-07 | 1986-01-30 | Uv curable high tensile strength resin composition |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4618632A (en) |
| JP (1) | JPS61183309A (en) |
| CN (1) | CN1004930B (en) |
| BR (1) | BR8600802A (en) |
| CA (1) | CA1245785A (en) |
| IN (1) | IN165383B (en) |
| NZ (1) | NZ215011A (en) |
| ZA (1) | ZA86529B (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63130611A (en) * | 1986-11-21 | 1988-06-02 | Nippon Kayaku Co Ltd | Polyurethane-(meth)acrylate mixture, resin composition and coating agent |
| US5213875A (en) * | 1987-09-30 | 1993-05-25 | Westinghouse Electric Corp. | UV conformal coatings |
| US4999136A (en) * | 1988-08-23 | 1991-03-12 | Westinghouse Electric Corp. | Ultraviolet curable conductive resin |
| US5114783A (en) * | 1988-08-23 | 1992-05-19 | Thor Radiation Research, Inc. | Protective coating system for imparting resistance to abrasion, impact and solvents |
| GB2226566B (en) * | 1988-12-12 | 1992-04-08 | Croda Applic Chemicals Limited | Automotive sealing process |
| US5013631A (en) * | 1989-03-03 | 1991-05-07 | Westinghouse Electric Corp. | Ultraviolet curable conformal coatings |
| US5206381A (en) * | 1989-08-07 | 1993-04-27 | Westinghouse Electric Corp. | Ultraviolet radiation curable polyamideimide oligomers |
| DE4306102A1 (en) * | 1993-02-27 | 1994-09-01 | Basf Lacke & Farben | Powder coatings based on polyesters containing carboxyl groups and suitable crosslinking agents as well as processes for coating metal sheets |
| US5763503A (en) * | 1995-06-07 | 1998-06-09 | Esschem, Inc. | Radiation-curable, moldable material, methods for curing it and molded articles obtained therefrom |
| SG48462A1 (en) * | 1995-10-26 | 1998-04-17 | Ibm | Lead protective coating composition process and structure thereof |
| GB9522656D0 (en) * | 1995-11-04 | 1996-01-03 | Zeneca Ltd | Mould |
| US6413351B1 (en) * | 1996-05-31 | 2002-07-02 | General Electric Company | Edge bonding for amorphous metal transformer |
| AU1519099A (en) * | 1997-11-04 | 1999-05-24 | Composite Technology Group, Llc | Nonstyrenated polyester and vinylester resins |
| DE19920799A1 (en) | 1999-05-06 | 2000-11-16 | Basf Coatings Ag | Coating material curable thermally and with actinic radiation and its use |
| DE19924674C2 (en) | 1999-05-29 | 2001-06-28 | Basf Coatings Ag | Coating material curable thermally and with actinic radiation and its use |
| WO2001030879A1 (en) * | 1999-10-26 | 2001-05-03 | Cook Composites And Polymers Company | Aromatic diol based urethaneacrylates and resin compositions containing the same having improved water and/or chemical resistance |
| DE10113884B4 (en) * | 2001-03-21 | 2005-06-02 | Basf Coatings Ag | Process for coating microporous surfaces and use of the process |
| US6852771B2 (en) * | 2001-08-28 | 2005-02-08 | Basf Corporation | Dual radiation/thermal cured coating composition |
| US20030077394A1 (en) * | 2001-08-28 | 2003-04-24 | Bradford Christophen J. | Dual cure coating composition and process for using the same |
| US6835759B2 (en) * | 2001-08-28 | 2004-12-28 | Basf Corporation | Dual cure coating composition and processes for using the same |
| DE10206225C1 (en) * | 2002-02-15 | 2003-09-18 | Basf Coatings Ag | Process for producing multicoat color and / or effect paint systems |
| DE10248324A1 (en) * | 2002-10-17 | 2004-05-06 | Basf Coatings Ag | Coating material curable thermally and with actinic radiation and process for coating micropoporous surfaces |
| US20050238884A1 (en) * | 2004-04-27 | 2005-10-27 | Peters David D | Urethane acrylate composition structure |
| US20060052524A1 (en) * | 2004-09-07 | 2006-03-09 | Peters David D | Urethane acrylate composition |
| US20060051590A1 (en) * | 2004-09-07 | 2006-03-09 | Peters David D | Urethane acrylate composition |
| US20050239991A1 (en) * | 2004-04-27 | 2005-10-27 | Basf Corporation. | Method of producing a urethane acrylate |
| US20050238883A1 (en) * | 2004-04-27 | 2005-10-27 | Peeler Calvin T | Urethane acrylate composite structure |
| US20060051593A1 (en) * | 2004-04-27 | 2006-03-09 | Peeler Calvin T | Urethane acrylate composite structure |
| US20050239955A1 (en) * | 2004-04-27 | 2005-10-27 | Basf Corporation. | Urethane acrylate composition structure |
| JP2009046205A (en) * | 2007-08-13 | 2009-03-05 | Koichi Kimura | Carriage |
| JP2014074158A (en) * | 2012-09-11 | 2014-04-24 | Nippon Synthetic Chem Ind Co Ltd:The | Active energy ray-curable resin composition and coating agent composition obtained using the same |
| CN114085332B (en) * | 2021-11-26 | 2023-08-08 | 上海华谊涂料有限公司 | High-solid hydroxyl acrylic resin and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780133A (en) * | 1968-10-30 | 1973-12-18 | Allied Chem | Diphenol containing polyesters derived from tris (2-hydroxyalkyl)isocyanurates |
| US3891523A (en) * | 1970-01-19 | 1975-06-24 | Dainippon Ink & Chemicals | Photopolymerizable, isocyanate-containing prepolymers |
| GB1453840A (en) * | 1973-05-15 | 1976-10-27 | Ici Ltd | Moulding composition |
| US4317858A (en) * | 1980-06-27 | 1982-03-02 | Westinghouse Electric Corp. | Ultraviolet curable solvent-free wire enamel blends |
| US4357219A (en) * | 1980-06-27 | 1982-11-02 | Westinghouse Electric Corp. | Solventless UV cured thermosetting cement coat |
| JPS5863760A (en) * | 1981-10-09 | 1983-04-15 | Nippon Paint Co Ltd | Photosetting coating composition |
| US4481258A (en) * | 1982-10-07 | 1984-11-06 | Westinghouse Electric Corp. | UV Curable composition and coil coatings |
-
1985
- 1985-02-07 US US06/699,373 patent/US4618632A/en not_active Expired - Fee Related
-
1986
- 1986-01-22 IN IN45/CAL/86A patent/IN165383B/en unknown
- 1986-01-23 ZA ZA86529A patent/ZA86529B/en unknown
- 1986-01-30 CA CA000500755A patent/CA1245785A/en not_active Expired
- 1986-02-03 NZ NZ215011A patent/NZ215011A/en unknown
- 1986-02-05 CN CN86100493.0A patent/CN1004930B/en not_active Expired
- 1986-02-06 JP JP61025652A patent/JPS61183309A/en active Pending
- 1986-02-07 BR BR8600802A patent/BR8600802A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN86100493A (en) | 1986-10-01 |
| JPS61183309A (en) | 1986-08-16 |
| NZ215011A (en) | 1989-06-28 |
| ZA86529B (en) | 1986-09-24 |
| IN165383B (en) | 1989-10-07 |
| US4618632A (en) | 1986-10-21 |
| BR8600802A (en) | 1986-11-04 |
| CN1004930B (en) | 1989-08-02 |
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