CA1337915C - Unsaturated polyester resin compositions and electrical laminates made therefrom - Google Patents
Unsaturated polyester resin compositions and electrical laminates made therefromInfo
- Publication number
- CA1337915C CA1337915C CA 587731 CA587731A CA1337915C CA 1337915 C CA1337915 C CA 1337915C CA 587731 CA587731 CA 587731 CA 587731 A CA587731 A CA 587731A CA 1337915 C CA1337915 C CA 1337915C
- Authority
- CA
- Canada
- Prior art keywords
- polyester
- polyoxyalkylene
- acid
- soft
- hard
- 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 - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31794—Of cross-linked polyester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3472—Woven fabric including an additional woven fabric layer
- Y10T442/3528—Three or more fabric layers
- Y10T442/3569—Woven fabric layers impregnated with a thermosetting resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3707—Woven fabric including a nonwoven fabric layer other than paper
- Y10T442/378—Coated, impregnated, or autogenously bonded
- Y10T442/3813—Coating or impregnation contains synthetic polymeric material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
- Y10T442/67—Multiple nonwoven fabric layers composed of the same inorganic strand or fiber material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
- Y10T442/671—Multiple nonwoven fabric layers composed of the same polymeric strand or fiber material
Abstract
An unsaturated polyester composition is provided comprising an unsaturate polyester component, a cross-linking monomer and as a modifier of the resin a polyoxyalkylene alcohol at least partially esterified with a polymerizable unsaturated carboxylic acid. The modifier is produced by esterifying the hydroxy group of a polyoxyalkylene mono- or polyalcohol at least partially with a polymerizable carboxylic acid such as maleic acid.
Description
UNSATURATED POLYESTER RESIN COMPOSITIONS AND ELECTRICAL
LAMINATES MADE THEREFROM
BACKGROUND OF THE INVENTION
This invention relates to an unsaturated polyester resin composition which is ~articularly useful in the manufacture of electrical laminates. The term "electrical laminates" as used herein refers to unclad insulation boards for mounting various electrical and electronic parts thereon as well as one or both sided metal clad laminates for use in the manufacture of printed circuit boards (PCBs). They are normally in the form of a flat sheet havinq a thickness of about 0.5-5 mm.
Electrical laminates made from unsaturated polyester resins are now commercially available and consumed in large quantities. These laminates are produced by pre-treating a cellulosic substrate with a melamine-type resin, imPregnating the substrate with a liquid unsaturated polyester resin, laminating a plurality of the resin-impregnated substrates, and curing the laminate. A continuous process for the production thereof is disclosed in U.S. Patent No. 4,372,800 assigned to the assignee of this application.
Unsaturated polyester resins in general find a variety of uses owing to their excellent mechanical properties and molding workability with various reinforcing materials. For *
LAMINATES MADE THEREFROM
BACKGROUND OF THE INVENTION
This invention relates to an unsaturated polyester resin composition which is ~articularly useful in the manufacture of electrical laminates. The term "electrical laminates" as used herein refers to unclad insulation boards for mounting various electrical and electronic parts thereon as well as one or both sided metal clad laminates for use in the manufacture of printed circuit boards (PCBs). They are normally in the form of a flat sheet havinq a thickness of about 0.5-5 mm.
Electrical laminates made from unsaturated polyester resins are now commercially available and consumed in large quantities. These laminates are produced by pre-treating a cellulosic substrate with a melamine-type resin, imPregnating the substrate with a liquid unsaturated polyester resin, laminating a plurality of the resin-impregnated substrates, and curing the laminate. A continuous process for the production thereof is disclosed in U.S. Patent No. 4,372,800 assigned to the assignee of this application.
Unsaturated polyester resins in general find a variety of uses owing to their excellent mechanical properties and molding workability with various reinforcing materials. For *
2 13379~5 use in the manufacture of PCBs, they must comply with high standard requirements for properties in terms of punching property, solder dip resistance, impact strength and the like. Needs exist for resins having an improved impact strength without deteriorating heat resistance in the field of large FRP products. These property requirements have become severer as automated processing of PCBs has become more popular and parts are packaged thereon more densely.
However, these requirements are often incompatible. For lo example, it has been difficult to improve both the heat resistance and impact strength simultaneously or to improve all of the low temperature-punchability, solder dip resistance and impact strength while keeping a good balance among them.
Attempts have been made to improve the impact strength by modifying unsaturated polyester resins with flexible resins, plasticizers, liquid butadiene-based polymers, cross-linked diene- or acrylic-based rubbers and the like. However, the incorporation of these modifiers is not satisfactory in that they tend to cause deterioration in heat resistance, chemical resistance, stability against phase separation, substrate-impregnating properties and other properties.
It is, therefore, a major object of the present invention to overcome the above-discussed problems.
Accordingly, the invention provides an unsaturated polyester resin composition comprising (a) a 1 3379 ~ 5 mixture of a hard unsaturated polyester and a soft unsaturated polyester, said soft polyester containing a polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof, said hard polyester being free from said polyoxyalkylene segment, (b) a crosslinking monomer, and (c) a polyoxyalkylene alcohol having an average molecular weight from 2000 to 8000 selected from the group consisting of a monoalcohol of which the hydroxyl groups are esterified to about 40 to 100 mole % with a polymerizable unsaturated carboxylic acid and a polyol of which the hydroxyl groups are esterified to about 20 to 70 mole ~ with a polymerizable unsaturated carboxylic acid.
The present invention also provides an electrical laminate comprising a plurality of layers of a fibrous substrate impregnated with the unsaturated polyester resin composition of the present invention.
Electrical laminates produced from the resin composition of the present invention exhibit improved impact strength and low-temperature punchability without deteriorating heat resistance and other properties.
As is well known, unsaturated polyesters are polycondensates of an ~,B-ethylenically unsaturated polycarboxylic acid optionally containing an unsaturated monocarboxylic acid and/or a polycarboxylic acid free from ethylenic unsaturation with a polyhydric alcohol optionally containing a monoalcohol. Unsaturated polyester resins are mixtures of the unsaturated polyester and a cross-linking monomer, typically styrene.
The unsaturated polyester composition of the present invention additionally contains, as a modifier of the unsaturated polyester resin, a partially esterified product of a hydroxy-terminated polyoxyalkylene compound.
Although any conventional unsaturated polyester resin may be modified by the present invention, an unsaturated polyester resin formulation containing a hard unsaturated polyester and a soft unsaturated polyester as disclosed in U.S. Patent No. 4,710,420 assigned to the assignee of this application is preferable. The soft polyester component contains a polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof, while the hard polyester component is free from said polyoxyalkylene segment.
'~
The hard polyester component may be prepared by reacting an unsaturated polycarboxylic acid, acid anhydride or mixtures thereof optionally containing an unsaturated monocarboxylic acid and/or a satutated polycarboxylic acid with a polyhydric alcohol optionally containing a mono alcohol.
Examples of unsaturated polycarboxylic acids and acid anhydrides include maleic anhydride and fllmaric acid.
The term "unsaturated" as used herein means an ethylenic unsaturation present between alpha and betA positions relative to the carboxyl group. Maleic acid dicyclopentadiene monoester (DCPD monomaleate) is an example of unsaturated monocarbocylic acid. Examples of saturated polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endic acid,trimellitic acid, pyromellitic acid, tetrabromophthalic acid, dibromoterephthalic acid, chlorendic acid, adipic acid, succinic acid, azelaic acid, sebacic acid and acid anhydrides of these acids. The term "saturated" as used herein means the absence of an ethylenic unsaturation between alpha and beta positions relative to the carboxyl group. It is desirable that the sum of unsaturated polycarboxylic acid and unsaturated monocarboxylic acid occupy from 40 to 100 mole % of the total acid reactants.
Examples of polyhydric alcohols includes ethylene - 6 - l 33791 5 glycol, propylene glycol, butanediol, neopentyl glycol, dlethylene glycol, dipropylene glycol, hexanediol, hydrogenated bisphenol A, glycerine, trimethylolpropane, pentaerythritol, dibromoneopentyl glycol, adducts of ethylene oxide or propylene oxide with bisphenol A, adducts of ethylene oxide or propylene oxide with tetrabromobisphenol A and bisphenol A epoxide. Examples of monoalcohols include hydroxylated dicyclopentadiene, ethylene glycol monomethyl ether, cinnamyl alcohol and stearyl alcohol.
For use in the manufacture of electrical laminates, the hard polyester component may preferably be flame retarded.
This may be effected by synthesizing the polyester using halogen-containing acid or alcohol components such as dibromophthalic acid, chlorendic acid, dibromoneopentyl glycol or adducts of ethylene oxide or propylene oxide with tetrabromobisphenol A. Alternatively an unsaturated polyester may be synthesized using as a part of acid and/or alcohol reactants a compound having a double bond to which a halogen molecule may preferentially be added. Thereafter the resulting polyester may be post-halogenated without haloge-nating ethylenic alpha, beta unsaturation. Examples of such acid and alcohol reactants include DCPD monomaleate, tetrahydrophthalic acid, hydroxylated DCPD and cinnamyl alcohol. In a preferred embodiment, the hard polyester component is prepared by post-br~minating an unsaturated polyester including a tetrahydrophthalic acid moiety in the middle of the polymer chain and a DCPD monomaleate moiety at each terminal of the polymer chain.
The soft polyester component used in the present invention may be prepared in the same way as the hard polyester component as discussed above except that the soft polyester component additionally contains an polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof. The incorporation of polyoxyalkylene segment may be effected by using as a part of alcohol reactants a polyoxyalkylene monoalcohol and/or a polyoxyalkylene polyol having a molecular weight of 600 to 6000, or by copolymerizing said polyoxyalkylene mono-and/or polyalcohol with an oligomer of unsaturated polyester free from the polyoxyalkylene segment. The polyoxyalkylene chain content of the soft polyester may range from 25 to 75 %, preferably from 25 to 50 %, more preferably from 25 to 40 % by weight. Examples of polyoxyalkylene chains include homopolymers of propylene oxide, copolymers of propylene oxide and ethylene oxide, copolymers of propylene oxide and tetramethylene oxide and copolymers of ethylene oxide and tetramethylene oxide. Polyoxypropylene mono- or polyalcohols are preferable. Preferably the soft polyester component also has a DCPD monomaleate moiety at each terminal. This increases its comPatibility with the hard ,1 ~
_ - 8 - 1337915 unsaturated polyester component and decreases the moisture absorption of the entire composition. The soft polyester component may or may not be post-haloganated for rendering flame retardant.
The modifier ester may be synthesized by esterifying polyoxyalkylene mono- or polyalcohols with a polymerizable unsaturated carboxylic acid by the conventional method.
The term "at least partially esterified" refers to about 20 to 80 mole %, preferably about 40 to 70 mole % of the hydroxy group possessed by the polyoxyalkylene polyols, and about 40 to 100 mole %, prefrably about 80 to 100 mole % of the hydroxy group possessed by the polyoxyalkylene monoalcohols are esterified with the polymerizable unsaturated carboxylic acid. Within these ranges of degree of esterification, the polyoxyalkylene ester exhibits a good compatibility with other components and the entire composition exhibits a reduced moisture absorption.
Examples of polyoxyalkylene alcohols include diols such as polyethylene glycols, polypropylene glycols, ethylene oxide-propylene oxide block or random copolymers; polyols having corresponding polyoxyalkylene chains derived from polyols such as glycerine, trimethylolpropane, pentaerythritol and the like, and monoethers and monoesters of the above polyoxyalkylene diols. The polyoxyalkylene alcohols preferably have an average molecular weight from 2000 to 8000. Examples of polymerizable unsaturated carboxylic acids includes acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride. Maleic anhydride is preferable. The reaction of maleic anhydride with-the polyoxyalkylene alcohol may be carried out at a temperature from 60C to 170C, preferably from 100C to 150C under normal or elevated pressures.
The completion of the esterification reaction may be determined by the acid number or viscosity of the reaction mixture. The reaction is preferably carried out under pressure for promoting the reaction and also for preventing sublimination of maleic anhydride. Care should be taken, however, that the reaction temperature does not exceed 170C
at which a polycondensation reaction begins to take place.
The modifier ester is added in an amount of 2 to 10 % by weight of the composition.
Examples of cross-linking monomers include styrene, ~- methylstyrene, vinyltoluene, p-methylstyrene, chlorostyrene, divinylbenzene, Cl 10 alkyl acrylates, Cl_10 alkyl methacrylate, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, diallyl phthalate, triallyl cyanurate and mixtures of these monomers. Styrene is most preferable.
The proportion of cross-linking monomer ranges between 10 and 70 %, preferably 20 and 50 % based on the combined weight of the nard polyester, the soft polyester, the - lo - 1 3379 1 5 modifier ester and the cross-linking monomer.
The proportions of the soft polyester component and the modifier ester in the entire resin composition are such that the total polyoxyalkylene chain content ranges from 5 to 30 %, preferably from 6 to 25 %, more preferably from 8 to 20 % based on the combined weight of the hard polyester, the soft polyester, the modifier and the cross-linking monomer.
The unsaturated resin composition of the present invention may contain conventional additives such as additive type flame retardants, fillers, antioxidants, stabilizers, other polymers, colorants and the like as desired. Examples of additive type flame retardants include phosphorus based flame retardants such as trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triethyl phosphite, triphenyl phosphite, tris-(chloroethyl)-phosphate and red phosphorus; halogenated flame retardants such as chlorinated paraffin, tetrabromobisphenol A and its derivatives, and tribormophenyl monoglycidyl ether;
antimony compounds such as antimony tri-or pentoxide and sodium antimonate; and other flame retardants such as zinc borate and aluminum hydroxide.
In order to promote the compatibity of the modifier component with other components, a small amount of substances such as polycaprolactone, saturated polyesters, vegetable oil derivatives, dimer acid derivatives, xylene resins and mixtures of these substances may be added.
The resin composition of the present invention may be cured using anyconventional peroxide catalyst.
Examples of preferred peroxide catalysts include peroxy ketals such as l,l-bis-(t-butylperoxY)-3,3,5-trimethyl-cyclohexane and l,l-bis-(t-butylperoxy)cyclohexane; and dialkyl peroxides such as di-t-butylperoxide; and peroxyesters such as t-butylperoxy benzoate. These catalysts may be incorporated in amounts from 0.5 to 2.0 parts per 100 parts by weight of the resin composition.
The resin composition may also be cured by irradiating with actinic radiation such as UV radiation, electron beam radiation and other radiation as desired by incorporating an appropriate curing catalyst.
The unsaturated resin composition of the present invention is highly suited for, but not limited to, the production of electrical laminates. In such use, a fibrous substrate or reinforcement is impregnated with the resin composition of the present invention. A plurality of resin-impregnated substrates are combined together optionally with a cladding metal foil being placed on one or both sides and the resulting laminate is cured. The entire operation may preferably be carried out in a continuous mode as described in the hereinbefore cited U.S. Pat. No. 4,372,800. Examples of substrates include glass substrates in the form of cloth, mat or paper; and cellulosic substrates such as kraft paper, or cotton linter paper. Cellulosic substrates pretreated with aminoplast resin are preferable.
The following examples will illustrate the present invention. All parts and percents therein are by weight unless oterwise indicated.
EXAMPLE
Soft unsaturated polyester resin (A) A one liter flask equipped with stirrer, thermometer, nitrogen gas-introducing tube, and distillation column was charged with 69.5 g of DCPD monomaleate, 165.8 g of bis(propyleneglycol)isophthalate, 136.4 g of bis(propylene-glycol)fumarate, 168 g of polvpropylene glycol(average M.W.=1200) and 82.4 g of maleic anhydride. The reaction was continued under nitrogen gas stream at an inner temperature of 150-200C until an acid number of 20 was reached. The reaction product was allowed to cool.
When the temperature was dropped to 160C., 90 mg of hydroquinone was added. When the temperature was dropped to 100C., an amount of styrene was added to a styrene content of 35 %.
Hard unsaturated polyester resin (B) A similar one liter flask was charged with 198.6 g of DCPD monomaleate, 236 g of bis(propyleneglycol)-fumarate, and 39.2 g of maleic anhydride. The reaction was continued at an inner temperature of 150-200 C., until an acid number of 20 was reached. The reaction product was allowed to cool. When the temperature was dropped to 160 C., 90 mg of hydroquinone was added. When the temperature was dropped to 100 C., an amount of styrene was added to a styrene content of 35%.
Modifier ester (C) A one liter flash equipped with stirrer, thermometer and nitrogen gas-introducing tube was charged with 700 g of a tri-functional polyoxyalkylene polyol having an average M.W. of 3500 (EP530 , MITSUI NISSO
POLYURETHANE CO., LTD.) and 29.4 g of maleic anhydride.
The reaction was continued at an inner temperature of 100-150 C., for 6 hours until an acid number of 24.3 was reached.
Production of copper clad laminate 50 parts of soft polyester resin (A), 50 parts of hard polyester (B), 5 parts of modifier (C) and 1 part of BPO (benzoyl peroxide) were thoroughly mixed to prepare an impregnating liquid resin.
A kraft paper having a thickness of 285 microns was pretreated with a methanolic solution of methylolmelamine *t rade-mark - 14 - 13379~5 and then dried. This paper substrate was impregnated with the above liquid resin. Five plies of the resin impregnated substrates and a 35 micron thickness copper foil having a coating of epoxy adhesive were laminated. The laminate was cured at 100C for 30 minutes to give a one sided copper clad laminate having a thickness of 1.6 mm. Properties of the laminate are shown in Table 1.
A one sided copper clad laminate having a thickness of 1.6 mm was produced as the laminate of Example using a resin composition consisting of 50 parts of soft polyester resin (A), 50 parts Of hard polyester resin (B) and 1 part of BPO. Properties of the laminate are shown in Table 1.
A one sided copper clad laminate having a thickness of 1.6 mm was produced as the laminate of Example using a resin composition consisting of 50 parts of soft polyester resin (A), 50 parts of hard polyester resin (B), 5 parts of unesterified polyoxyalkylene polyol EP530 and 1 part of BPO. Properties of the laminate are shown in Table 1.
.~
~ ~ s s ~ s o o ~ o C
Q
o O O ~ O O
S~ X a~ O o o\
O ~ ~ U~
~ ~ O
Ei ~ u~ ~ ~ 3 O O aJ 3 U Z aJ ~ ~
~ ~ O
O ~1 ,~
o ~ O O ~
X O ~ O O 1 S
~ ~ o O O U~
E~
However, these requirements are often incompatible. For lo example, it has been difficult to improve both the heat resistance and impact strength simultaneously or to improve all of the low temperature-punchability, solder dip resistance and impact strength while keeping a good balance among them.
Attempts have been made to improve the impact strength by modifying unsaturated polyester resins with flexible resins, plasticizers, liquid butadiene-based polymers, cross-linked diene- or acrylic-based rubbers and the like. However, the incorporation of these modifiers is not satisfactory in that they tend to cause deterioration in heat resistance, chemical resistance, stability against phase separation, substrate-impregnating properties and other properties.
It is, therefore, a major object of the present invention to overcome the above-discussed problems.
Accordingly, the invention provides an unsaturated polyester resin composition comprising (a) a 1 3379 ~ 5 mixture of a hard unsaturated polyester and a soft unsaturated polyester, said soft polyester containing a polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof, said hard polyester being free from said polyoxyalkylene segment, (b) a crosslinking monomer, and (c) a polyoxyalkylene alcohol having an average molecular weight from 2000 to 8000 selected from the group consisting of a monoalcohol of which the hydroxyl groups are esterified to about 40 to 100 mole % with a polymerizable unsaturated carboxylic acid and a polyol of which the hydroxyl groups are esterified to about 20 to 70 mole ~ with a polymerizable unsaturated carboxylic acid.
The present invention also provides an electrical laminate comprising a plurality of layers of a fibrous substrate impregnated with the unsaturated polyester resin composition of the present invention.
Electrical laminates produced from the resin composition of the present invention exhibit improved impact strength and low-temperature punchability without deteriorating heat resistance and other properties.
As is well known, unsaturated polyesters are polycondensates of an ~,B-ethylenically unsaturated polycarboxylic acid optionally containing an unsaturated monocarboxylic acid and/or a polycarboxylic acid free from ethylenic unsaturation with a polyhydric alcohol optionally containing a monoalcohol. Unsaturated polyester resins are mixtures of the unsaturated polyester and a cross-linking monomer, typically styrene.
The unsaturated polyester composition of the present invention additionally contains, as a modifier of the unsaturated polyester resin, a partially esterified product of a hydroxy-terminated polyoxyalkylene compound.
Although any conventional unsaturated polyester resin may be modified by the present invention, an unsaturated polyester resin formulation containing a hard unsaturated polyester and a soft unsaturated polyester as disclosed in U.S. Patent No. 4,710,420 assigned to the assignee of this application is preferable. The soft polyester component contains a polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof, while the hard polyester component is free from said polyoxyalkylene segment.
'~
The hard polyester component may be prepared by reacting an unsaturated polycarboxylic acid, acid anhydride or mixtures thereof optionally containing an unsaturated monocarboxylic acid and/or a satutated polycarboxylic acid with a polyhydric alcohol optionally containing a mono alcohol.
Examples of unsaturated polycarboxylic acids and acid anhydrides include maleic anhydride and fllmaric acid.
The term "unsaturated" as used herein means an ethylenic unsaturation present between alpha and betA positions relative to the carboxyl group. Maleic acid dicyclopentadiene monoester (DCPD monomaleate) is an example of unsaturated monocarbocylic acid. Examples of saturated polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endic acid,trimellitic acid, pyromellitic acid, tetrabromophthalic acid, dibromoterephthalic acid, chlorendic acid, adipic acid, succinic acid, azelaic acid, sebacic acid and acid anhydrides of these acids. The term "saturated" as used herein means the absence of an ethylenic unsaturation between alpha and beta positions relative to the carboxyl group. It is desirable that the sum of unsaturated polycarboxylic acid and unsaturated monocarboxylic acid occupy from 40 to 100 mole % of the total acid reactants.
Examples of polyhydric alcohols includes ethylene - 6 - l 33791 5 glycol, propylene glycol, butanediol, neopentyl glycol, dlethylene glycol, dipropylene glycol, hexanediol, hydrogenated bisphenol A, glycerine, trimethylolpropane, pentaerythritol, dibromoneopentyl glycol, adducts of ethylene oxide or propylene oxide with bisphenol A, adducts of ethylene oxide or propylene oxide with tetrabromobisphenol A and bisphenol A epoxide. Examples of monoalcohols include hydroxylated dicyclopentadiene, ethylene glycol monomethyl ether, cinnamyl alcohol and stearyl alcohol.
For use in the manufacture of electrical laminates, the hard polyester component may preferably be flame retarded.
This may be effected by synthesizing the polyester using halogen-containing acid or alcohol components such as dibromophthalic acid, chlorendic acid, dibromoneopentyl glycol or adducts of ethylene oxide or propylene oxide with tetrabromobisphenol A. Alternatively an unsaturated polyester may be synthesized using as a part of acid and/or alcohol reactants a compound having a double bond to which a halogen molecule may preferentially be added. Thereafter the resulting polyester may be post-halogenated without haloge-nating ethylenic alpha, beta unsaturation. Examples of such acid and alcohol reactants include DCPD monomaleate, tetrahydrophthalic acid, hydroxylated DCPD and cinnamyl alcohol. In a preferred embodiment, the hard polyester component is prepared by post-br~minating an unsaturated polyester including a tetrahydrophthalic acid moiety in the middle of the polymer chain and a DCPD monomaleate moiety at each terminal of the polymer chain.
The soft polyester component used in the present invention may be prepared in the same way as the hard polyester component as discussed above except that the soft polyester component additionally contains an polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof. The incorporation of polyoxyalkylene segment may be effected by using as a part of alcohol reactants a polyoxyalkylene monoalcohol and/or a polyoxyalkylene polyol having a molecular weight of 600 to 6000, or by copolymerizing said polyoxyalkylene mono-and/or polyalcohol with an oligomer of unsaturated polyester free from the polyoxyalkylene segment. The polyoxyalkylene chain content of the soft polyester may range from 25 to 75 %, preferably from 25 to 50 %, more preferably from 25 to 40 % by weight. Examples of polyoxyalkylene chains include homopolymers of propylene oxide, copolymers of propylene oxide and ethylene oxide, copolymers of propylene oxide and tetramethylene oxide and copolymers of ethylene oxide and tetramethylene oxide. Polyoxypropylene mono- or polyalcohols are preferable. Preferably the soft polyester component also has a DCPD monomaleate moiety at each terminal. This increases its comPatibility with the hard ,1 ~
_ - 8 - 1337915 unsaturated polyester component and decreases the moisture absorption of the entire composition. The soft polyester component may or may not be post-haloganated for rendering flame retardant.
The modifier ester may be synthesized by esterifying polyoxyalkylene mono- or polyalcohols with a polymerizable unsaturated carboxylic acid by the conventional method.
The term "at least partially esterified" refers to about 20 to 80 mole %, preferably about 40 to 70 mole % of the hydroxy group possessed by the polyoxyalkylene polyols, and about 40 to 100 mole %, prefrably about 80 to 100 mole % of the hydroxy group possessed by the polyoxyalkylene monoalcohols are esterified with the polymerizable unsaturated carboxylic acid. Within these ranges of degree of esterification, the polyoxyalkylene ester exhibits a good compatibility with other components and the entire composition exhibits a reduced moisture absorption.
Examples of polyoxyalkylene alcohols include diols such as polyethylene glycols, polypropylene glycols, ethylene oxide-propylene oxide block or random copolymers; polyols having corresponding polyoxyalkylene chains derived from polyols such as glycerine, trimethylolpropane, pentaerythritol and the like, and monoethers and monoesters of the above polyoxyalkylene diols. The polyoxyalkylene alcohols preferably have an average molecular weight from 2000 to 8000. Examples of polymerizable unsaturated carboxylic acids includes acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride. Maleic anhydride is preferable. The reaction of maleic anhydride with-the polyoxyalkylene alcohol may be carried out at a temperature from 60C to 170C, preferably from 100C to 150C under normal or elevated pressures.
The completion of the esterification reaction may be determined by the acid number or viscosity of the reaction mixture. The reaction is preferably carried out under pressure for promoting the reaction and also for preventing sublimination of maleic anhydride. Care should be taken, however, that the reaction temperature does not exceed 170C
at which a polycondensation reaction begins to take place.
The modifier ester is added in an amount of 2 to 10 % by weight of the composition.
Examples of cross-linking monomers include styrene, ~- methylstyrene, vinyltoluene, p-methylstyrene, chlorostyrene, divinylbenzene, Cl 10 alkyl acrylates, Cl_10 alkyl methacrylate, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, diallyl phthalate, triallyl cyanurate and mixtures of these monomers. Styrene is most preferable.
The proportion of cross-linking monomer ranges between 10 and 70 %, preferably 20 and 50 % based on the combined weight of the nard polyester, the soft polyester, the - lo - 1 3379 1 5 modifier ester and the cross-linking monomer.
The proportions of the soft polyester component and the modifier ester in the entire resin composition are such that the total polyoxyalkylene chain content ranges from 5 to 30 %, preferably from 6 to 25 %, more preferably from 8 to 20 % based on the combined weight of the hard polyester, the soft polyester, the modifier and the cross-linking monomer.
The unsaturated resin composition of the present invention may contain conventional additives such as additive type flame retardants, fillers, antioxidants, stabilizers, other polymers, colorants and the like as desired. Examples of additive type flame retardants include phosphorus based flame retardants such as trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triethyl phosphite, triphenyl phosphite, tris-(chloroethyl)-phosphate and red phosphorus; halogenated flame retardants such as chlorinated paraffin, tetrabromobisphenol A and its derivatives, and tribormophenyl monoglycidyl ether;
antimony compounds such as antimony tri-or pentoxide and sodium antimonate; and other flame retardants such as zinc borate and aluminum hydroxide.
In order to promote the compatibity of the modifier component with other components, a small amount of substances such as polycaprolactone, saturated polyesters, vegetable oil derivatives, dimer acid derivatives, xylene resins and mixtures of these substances may be added.
The resin composition of the present invention may be cured using anyconventional peroxide catalyst.
Examples of preferred peroxide catalysts include peroxy ketals such as l,l-bis-(t-butylperoxY)-3,3,5-trimethyl-cyclohexane and l,l-bis-(t-butylperoxy)cyclohexane; and dialkyl peroxides such as di-t-butylperoxide; and peroxyesters such as t-butylperoxy benzoate. These catalysts may be incorporated in amounts from 0.5 to 2.0 parts per 100 parts by weight of the resin composition.
The resin composition may also be cured by irradiating with actinic radiation such as UV radiation, electron beam radiation and other radiation as desired by incorporating an appropriate curing catalyst.
The unsaturated resin composition of the present invention is highly suited for, but not limited to, the production of electrical laminates. In such use, a fibrous substrate or reinforcement is impregnated with the resin composition of the present invention. A plurality of resin-impregnated substrates are combined together optionally with a cladding metal foil being placed on one or both sides and the resulting laminate is cured. The entire operation may preferably be carried out in a continuous mode as described in the hereinbefore cited U.S. Pat. No. 4,372,800. Examples of substrates include glass substrates in the form of cloth, mat or paper; and cellulosic substrates such as kraft paper, or cotton linter paper. Cellulosic substrates pretreated with aminoplast resin are preferable.
The following examples will illustrate the present invention. All parts and percents therein are by weight unless oterwise indicated.
EXAMPLE
Soft unsaturated polyester resin (A) A one liter flask equipped with stirrer, thermometer, nitrogen gas-introducing tube, and distillation column was charged with 69.5 g of DCPD monomaleate, 165.8 g of bis(propyleneglycol)isophthalate, 136.4 g of bis(propylene-glycol)fumarate, 168 g of polvpropylene glycol(average M.W.=1200) and 82.4 g of maleic anhydride. The reaction was continued under nitrogen gas stream at an inner temperature of 150-200C until an acid number of 20 was reached. The reaction product was allowed to cool.
When the temperature was dropped to 160C., 90 mg of hydroquinone was added. When the temperature was dropped to 100C., an amount of styrene was added to a styrene content of 35 %.
Hard unsaturated polyester resin (B) A similar one liter flask was charged with 198.6 g of DCPD monomaleate, 236 g of bis(propyleneglycol)-fumarate, and 39.2 g of maleic anhydride. The reaction was continued at an inner temperature of 150-200 C., until an acid number of 20 was reached. The reaction product was allowed to cool. When the temperature was dropped to 160 C., 90 mg of hydroquinone was added. When the temperature was dropped to 100 C., an amount of styrene was added to a styrene content of 35%.
Modifier ester (C) A one liter flash equipped with stirrer, thermometer and nitrogen gas-introducing tube was charged with 700 g of a tri-functional polyoxyalkylene polyol having an average M.W. of 3500 (EP530 , MITSUI NISSO
POLYURETHANE CO., LTD.) and 29.4 g of maleic anhydride.
The reaction was continued at an inner temperature of 100-150 C., for 6 hours until an acid number of 24.3 was reached.
Production of copper clad laminate 50 parts of soft polyester resin (A), 50 parts of hard polyester (B), 5 parts of modifier (C) and 1 part of BPO (benzoyl peroxide) were thoroughly mixed to prepare an impregnating liquid resin.
A kraft paper having a thickness of 285 microns was pretreated with a methanolic solution of methylolmelamine *t rade-mark - 14 - 13379~5 and then dried. This paper substrate was impregnated with the above liquid resin. Five plies of the resin impregnated substrates and a 35 micron thickness copper foil having a coating of epoxy adhesive were laminated. The laminate was cured at 100C for 30 minutes to give a one sided copper clad laminate having a thickness of 1.6 mm. Properties of the laminate are shown in Table 1.
A one sided copper clad laminate having a thickness of 1.6 mm was produced as the laminate of Example using a resin composition consisting of 50 parts of soft polyester resin (A), 50 parts Of hard polyester resin (B) and 1 part of BPO. Properties of the laminate are shown in Table 1.
A one sided copper clad laminate having a thickness of 1.6 mm was produced as the laminate of Example using a resin composition consisting of 50 parts of soft polyester resin (A), 50 parts of hard polyester resin (B), 5 parts of unesterified polyoxyalkylene polyol EP530 and 1 part of BPO. Properties of the laminate are shown in Table 1.
.~
~ ~ s s ~ s o o ~ o C
Q
o O O ~ O O
S~ X a~ O o o\
O ~ ~ U~
~ ~ O
Ei ~ u~ ~ ~ 3 O O aJ 3 U Z aJ ~ ~
~ ~ O
O ~1 ,~
o ~ O O ~
X O ~ O O 1 S
~ ~ o O O U~
E~
3 ~ o O u~ h ~ Ql r~ r~ Q u~ ~
E- Ei O O O O a) u O ~ O O
x ~ / 3 ~:
a) aJ a s o aJ
~ a ~0 X ~ S S O-.
C' U ~ ~ S .
J ~ ~ ~ ~ a) -, ~ o O-- ~1 Q ~ ~ S
~) t~ o ~ J
- ~1~'~1 Q ~ H td ~ C) O S
~ o~~ s ~ m o u~ ~o ~3 ~ ~-- -- --~o ~ o'~ ~ Q C) As can been seen from Table l, the laminate of Example exhibited excellent impact strength and low temperature-punchability when comparing with the laminate of Comparative Example 1 which is free from the modifier (C).
It also exhibited excellent solvent resistance when comparing with the laminate of Comparative Example 2 which contains a free polyoxyalkylene polyol corresponding to the modifier (C).
E- Ei O O O O a) u O ~ O O
x ~ / 3 ~:
a) aJ a s o aJ
~ a ~0 X ~ S S O-.
C' U ~ ~ S .
J ~ ~ ~ ~ a) -, ~ o O-- ~1 Q ~ ~ S
~) t~ o ~ J
- ~1~'~1 Q ~ H td ~ C) O S
~ o~~ s ~ m o u~ ~o ~3 ~ ~-- -- --~o ~ o'~ ~ Q C) As can been seen from Table l, the laminate of Example exhibited excellent impact strength and low temperature-punchability when comparing with the laminate of Comparative Example 1 which is free from the modifier (C).
It also exhibited excellent solvent resistance when comparing with the laminate of Comparative Example 2 which contains a free polyoxyalkylene polyol corresponding to the modifier (C).
Claims (8)
1. An unsaturated polyester resin composition comprising (a) a mixture of a hard unsaturated polyester and a soft unsaturated polyester, said soft polyester containing a polyoxyalkylene segment having a molecular weight from 600 to 6000 in the backbone thereof, said hard polyester being free from said polyoxyalkylene segment, (b) a crosslinking monomer, and (c) a polyoxyalkylene alcohol having an average molecular weight from 2000 to 8000 selected from the group consisting of a monoalcohol of which the hydroxyl groups are esterified to about 40 to 100 mole % with a polymerizable unsaturated carboxylic acid and a polyol of which the hydroxyl groups are esterified to about 20 to 70 mole % with a polymerizable unsaturated carboxylic acid.
2. A composition according to claim 1, wherein said polymerizable unsaturated carboxylic acid is maleic acid.
3. A composition according to claim 1, wherein said polyoxyalkylene alcohol (c) is present in an amount from 2 to 10% by weight of the sum of said hard polyester, said soft polyester, said crosslinking monomer and said polyoxyalkylene alcohol ester.
4. A composition according to claim 1, wherein said soft polyester contains from 25 to 75% by weight of said polyoxyalkylene segment.
5. A composition according to claim 1, wherein the proportions of said soft polyester and said polyoxyalkylene alcohol therein are such that the total polyoxyalkylene content of said composition is from 5 to 30% by weight of the sum of said hard polyester, said soft polyester, said crosslinking monomer and said polyoxyalkylene alcohol ester.
6. A composition according to claim 1, wherein said composition contains said crosslinking monomer in an amount from 10 to 70% by weight of the sum of the hard polyester, the soft polyester, said crosslinking monomer and said polyoxyalkylene alcohol.
7. A composition according to claim 1, wherein said hard polyester is post-halogenated.
8. An electrical laminate comprising a plurality of layers of fibrous substrate impregnated with the resin composition of claim 1, 2, 3, 4, 5, 6 or 7.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17807087A JPS6420219A (en) | 1987-07-15 | 1987-07-15 | Unsaturated polyester resin composition and laminate for electrical use |
| CA 587731 CA1337915C (en) | 1987-07-15 | 1989-01-09 | Unsaturated polyester resin compositions and electrical laminates made therefrom |
| US07/296,159 US4943474A (en) | 1987-07-15 | 1989-01-12 | Unsaturated polyester resin compositions and electrical laminates made therefrom |
| EP19890100586 EP0377769A1 (en) | 1987-07-15 | 1989-01-13 | Unsaturated polyester resin compositions and electrical laminates made therefrom |
| US07/520,498 US4990397A (en) | 1987-07-15 | 1990-05-03 | Unsaturated polyester resin compositions and electrical laminates made therefrom |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17807087A JPS6420219A (en) | 1987-07-15 | 1987-07-15 | Unsaturated polyester resin composition and laminate for electrical use |
| CA 587731 CA1337915C (en) | 1987-07-15 | 1989-01-09 | Unsaturated polyester resin compositions and electrical laminates made therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1337915C true CA1337915C (en) | 1996-01-09 |
Family
ID=25672366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 587731 Expired - Fee Related CA1337915C (en) | 1987-07-15 | 1989-01-09 | Unsaturated polyester resin compositions and electrical laminates made therefrom |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US4943474A (en) |
| EP (1) | EP0377769A1 (en) |
| JP (1) | JPS6420219A (en) |
| CA (1) | CA1337915C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162401A (en) * | 1989-10-30 | 1992-11-10 | Owens-Corning Fiberglas Corporation | Unsaturated polyester resin compositions containing compatible compounds |
| US5456947A (en) * | 1991-02-19 | 1995-10-10 | Fibre Glass-Evercoat Company, Inc. | Unsaturated polyester resins for curable polyester resin systems having improved adhesion to substrates |
| US5256709A (en) * | 1991-07-22 | 1993-10-26 | Owens-Corning Fiberglas Technology, Inc. | Unsaturated polyester resin compositions containing compatible compounds having aromatic substituents |
| US5256708A (en) * | 1991-07-22 | 1993-10-26 | Owens-Corning Fiberglas Technology, Inc. | Unsaturated polyester resin compositions containing compatible compounds having sulfur-containing substituents |
| US5298314A (en) * | 1991-09-10 | 1994-03-29 | Glasteel Industrial Laminates, Inc. | MC4 unsaturated polyester resin system |
| US5312691A (en) * | 1991-09-10 | 1994-05-17 | Glasteel Industrial Laminates, Inc. | Copper-clad MC4 unsaturated polyester resin |
| US5684086A (en) | 1995-07-28 | 1997-11-04 | Arco Chemical Technology, Inc. | Cured thermosets and glass-reinforced composites from unsaturated polyetherester resins |
| ES2171048T3 (en) | 1997-10-10 | 2002-08-16 | Cook Composites & Polymers | COMPOSITIONS OF UNSATURATED POLYESTER RESINS, WATER RESISTANT. |
| WO2000002971A1 (en) * | 1998-07-10 | 2000-01-20 | Reichhold, Inc. | Structural adhesive resin composition |
| JP4379854B2 (en) * | 2001-10-30 | 2009-12-09 | 日鉱金属株式会社 | Surface treated copper foil |
| DE102004028417A1 (en) * | 2004-06-11 | 2006-01-05 | Altana Electrical Insulation Gmbh | impregnating resin |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE923392C (en) * | 1952-10-02 | 1955-02-10 | Basf Ag | Process for the production of copolymers |
| DE1110409B (en) * | 1960-01-16 | 1961-07-06 | Basf Ag | Process for the production of solvent-resistant and flexible polymerisation products from unsaturated polyester resins |
| DE1669714A1 (en) * | 1967-08-18 | 1969-10-30 | Basf Ag | Process for producing molded articles from polyester molding compounds |
| JPS5698136A (en) * | 1980-01-08 | 1981-08-07 | Kanegafuchi Chem Ind Co Ltd | Continuous manufacture of laminated substance |
| EP0070755B1 (en) * | 1981-07-10 | 1986-02-12 | CdF CHIMIE RESINES | Curable polyester compounds |
| US4414367A (en) * | 1981-09-30 | 1983-11-08 | Union Carbide Corporation | Curable molding compositions |
| FR2529558B1 (en) * | 1982-06-30 | 1985-10-25 | Chloe Chemie | CURABLE POLYESTER COMPOSITIONS |
| US4710420A (en) * | 1984-12-21 | 1987-12-01 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Unsaturated polyester resin compositions |
-
1987
- 1987-07-15 JP JP17807087A patent/JPS6420219A/en active Pending
-
1989
- 1989-01-09 CA CA 587731 patent/CA1337915C/en not_active Expired - Fee Related
- 1989-01-12 US US07/296,159 patent/US4943474A/en not_active Expired - Fee Related
- 1989-01-13 EP EP19890100586 patent/EP0377769A1/en not_active Withdrawn
-
1990
- 1990-05-03 US US07/520,498 patent/US4990397A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0377769A1 (en) | 1990-07-18 |
| US4943474A (en) | 1990-07-24 |
| US4990397A (en) | 1991-02-05 |
| JPS6420219A (en) | 1989-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0186165B1 (en) | Unsaturated polyester resin compositions | |
| CA1337915C (en) | Unsaturated polyester resin compositions and electrical laminates made therefrom | |
| JP5164092B2 (en) | Thermosetting composition and cured product thereof | |
| US5116670A (en) | Allyl ester resin composition and laminated sheet using the same | |
| US4990409A (en) | Flame retardant electrical laminate | |
| CA1228443A (en) | Unsaturated polyester resin composition and laminates | |
| US5270104A (en) | Unsaturated polyester resin composition and laminates | |
| EP0094650B1 (en) | Flame-retardant halogen-containing unsaturated alkyds resins and articles made therefrom | |
| US5238730A (en) | Electrical laminate with dibasic acid-modified epoxy (meth)acrylate | |
| EP0336266B1 (en) | Electrical laminate produced by using special thermosetting resin compostions | |
| JPH0236218A (en) | Thermosetting resin composition and laminated sheet for electric use | |
| JP2000309697A (en) | Flame-retardant unsaturated polyester, resin containing the same, and cured product thereof | |
| JPH0559597B2 (en) | ||
| JPH0635534B2 (en) | Unsaturated polyester resin composition for electrical laminates | |
| KR950011045B1 (en) | Method of forming a electric layer-board | |
| JPS59166519A (en) | Flame-retardant unsaturated polyester resin composition and molded article thereof | |
| JPH07216053A (en) | High-molecular unsaturated polyester resin composition and its use | |
| JPH03182515A (en) | Laminating resin composition | |
| JPS606715A (en) | Unsaturated polyester resin composition and laminated sheet | |
| JPH0770290A (en) | High molecular weight unsaturated polyester resin composition and its use | |
| JPS5930813A (en) | Flame-retardant unsaturated polyester resin composition and laminated board | |
| JPH0251446B2 (en) | ||
| JPH03182514A (en) | Laminating resin composition | |
| JPS6274913A (en) | Curable resin composition | |
| JPH0588723B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |