Source: http://www.google.com/patents/US7364672?dq=5920316
Timestamp: 2013-12-13 23:03:01
Document Index: 334376760

Matched Legal Cases: ['arts 5013', 'arts 6017', 'arts 6017', 'arts 6017', 'arts 5013', 'arts 5013']

Patent US7364672 - Low loss prepregs, compositions useful for the preparation thereof and uses ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsIn accordance with the present invention, we have developed compositions useful for the preparation of prepregs, laminates, and the like having excellent performance properties. Invention compositions comprise a combination of a first component (i.e., a low loss, low dielectric constant, hydrocarbyl...http://www.google.com/patents/US7364672?utm_source=gb-gplus-sharePatent US7364672 - Low loss prepregs, compositions useful for the preparation thereof and uses thereforAdvanced Patent SearchPublication numberUS7364672 B2Publication typeGrantApplication numberUS 11/006,211Publication dateApr 29, 2008Filing dateDec 6, 2004Priority dateDec 6, 2004Fee statusPaidAlso published asCN101111556A, EP1828305A1, EP1828305A4, US20060118766, WO2006062879A1Publication number006211, 11006211, US 7364672 B2, US 7364672B2, US-B2-7364672, US7364672 B2, US7364672B2InventorsThomas Allan Koes, Ousama NajjarOriginal AssigneeArlon, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (101), Referenced by (2), Classifications (13), Legal Events (11) External Links: USPTO, USPTO Assignment, EspacenetLow loss prepregs, compositions useful for the preparation thereof and uses thereforUS 7364672 B2Abstract In accordance with the present invention, we have developed compositions useful for the preparation of prepregs, laminates, and the like having excellent performance properties. Invention compositions comprise a combination of a first component (i.e., a low loss, low dielectric constant, hydrocarbyl thermoplastic resin), a second component (i.e., a component which is capable of crosslinking to produce a thermoset in the presence of the first component), a free radical source, and optionally, one or more additives and/or diluents. Invention compositions can be prepared from widely available and inexpensive starting materials. As a result, invention compositions not only provide fabricated articles having outstanding performance properties, in addition, the cost of producing the resulting articles compares quite favorably with the cost of making competitive materials which require the use of more expensive, less readily available starting materials. Also provided in accordance with the present invention are prepregs prepared from invention compositions, laminated sheets prepared from the above-described prepregs, printed wiring boards, methods of making each of the above, and the like.
3. The composition of claim 1 wherein said composition, after cure, has a glass transition temperature ≧80� C.
each Q, when present, is independently selected from �CH2�, �O�, �O�C(O)�, �C(O)� or �C(O)�O�, and
12. The composition of claim 11 wherein Y is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and technically feasible combinations of any of the above with a linker selected from the group consisting of a covalent bond, �O�, �S�, �NR�, �O�C(O)�, �O�C(O)�O�, �O�C(O)�NR�, �NR�C(O)�, �NR�C(O)�O�, �NR�C(O)�NR�, �S�C(O)�, �S�C(O)�O�, �S�C(O)�NR�, �O�S(O)2�, �O�S(O)2�O�, �O�S(O)2�NR�, �O�S(O)�, �O�S(O)�O�, �O�S(O)�NR�, �O�NR�C(O)�, �O�NR�C(O)�O�, �O�NR�C(O)�NR�, �NR�O�C(O)�, �NR�O�C(O)�O�, �NR�O�C(O)�NR�, �O�NR�C(S)�, �O�NR�C(S)�O�, �O�NR�C(S)�NR�, �NR�O�C(S)�, �NR�O�C(S)�O�, �NR�O�C(S)�NR�, �O�C(S)�, �O�C(S)�O�, �O�C(S)�NR�, �NR�C(S)�, �NR�C(S)�O�, �NR�C(S)�NR�, �S�S(O)2�, �S�S(O)2�O�, �S�S(O)2�NR�, �NR�O�S(O)�, �NR�O�S(O)�O�, �NR�O�S(O)�NR�, �NR�O�S(O)2�, �NR�O�S(O)2�O�, �NR�O�S(O)2�NR�, �O�NR�S(O)�, �O�NR�S(O)�O�, �O�NR�S(O)�NR�, �O�NR�S(O)2�O�, �O�NR�S(O)2�NR�, �O�NR�S(O)2�, �O�P(O)R2�, �S�P(O)R2�, �NR�P(O)R2�;
17. The composition of claim 16 wherein (c) is a peroxide having a decomposition temperature of at least about 35� C.
FIELD OF THE INVENTION The present invention relates to prepregs, laminates and compositions useful for the preparation thereof. Invention materials are useful, for example, in the preparation of components used in RF applications, applications where low electrical loss products are required, e.g., in cellular telecommunications, laminate-based chip carriers, and the like.
BACKGROUND OF THE INVENTION Laminates and prepreg systems employed in cellular telecommunications, laminate-based chip carriers, and the like, must meet a number of physical and electrical performance criteria, e.g., low loss, low dielectric constant, good heat resistance, good dimensional stability, and the like. In view of the high demand and widespread use of such materials, in addition to meeting the above-described performance properties, it is further desirable that such materials are capable of being prepared from relatively inexpensive starting materials employing readily scalable, low cost processes. The present invention addresses these and other needs as described in greater detail herein.
SUMMARY OF THE INVENTION In accordance with the present invention, we have developed compositions useful for the preparation of prepregs, laminates, and the like having excellent performance properties. Invention compositions comprise a combination of a first component (i.e., a low loss, low dielectric constant, hydrocarbyl thermoplastic resin), a second component (i.e., a component which is capable of crosslinking to produce a thermoset in the presence of the first component), a free radical source, and optionally, one or more additives and/or diluents.
DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, there are provided compositions comprising:
(a) a first component comprising a low loss, low dielectric constant, hydrocarbyl thermoplastic resin, (b) a second component which is capable of crosslinking to produce a thermoset in the presence of the first component, (c) a free radical source, (d) optionally, one or more additives, and (e) an optional diluent therefor. As employed herein, the term �low loss� refers to materials which cause minimal signal loss when associated with signal transmission.
As employed herein, the term �low dielectric constant� refers to materials which resist the passage of electric current therethrough.
As employed herein, the term �hydrocarbyl thermoplastic resins� refers to polymeric materials which are prepared from non-heteroatom containing, unsaturated hydrocarbons, e.g., polyolefins, co-polymers including olefin monomers, cyclic olefin monomers, and the like, terpolymers, block copolymers, and the like.
Low loss, low dielectric constant, hydrocarbyl thermoplastic resins contemplated for use in the practice of the present invention can be characterized, for example, as materials which, when laminated, have a dielectric constant ≦4.5 nominal, and an electrical loss tangent ≦0.02. Additionally, such materials contemplated for use in the practice of the present invention may further be characterized as having a glass transition temperature ≧80� C.
q is an integer between 1 and 6, provided, however, that not all q's are 1, each R is independently selected from hydrogen or lower alkyl, each Q, when present, is independently selected from �CH2�, �O�, �O�C(O)�, �C(O)� or �C(O)�O�, and each Y is independently a monovalent or polyvalent moiety, provided, however, that not all Y's are monovalent. Monovalent or polyvalent Y can be selected from among many possibilities, such as, for example, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and technically feasible combinations of any of the above with a linker selected from the group consisting of a covalent bond, �O�, �S�, �NR�, �O�C(O)�, �O�C(O)�O�, �O�C(O)�NR�, �NR�C(O)�, �NR�C(O)�O�, �NR�C(O)�NR�, �S�C(O)�, �S�C(O)�O�, �S�C(O)�NR�, �O�S(O)2�, �O�S(O)2�O�, �O�S(O)2�NR�, �O�S(O)�, �O�S(O)�O�, �O�S(O)�NR�, �O�NR�C(O)�, �O�NR�C(O)�O�, �O�NR�C(O)�NR�, �NR�O�C(O)�, �NR�O�C(O)�O�, �NR�O�C(O)�NR�, �O�NR�C(S)�, �O�NR�C(S)�O�, �O�NR�C(S)�NR�, �NR�O�C(S)�, �NR�O�C(S)�O�, �NR�O�C(S)�NR�, �O�C(S)�, �O�C(S)�O�, �O�C(S)�NR�, �NR�C(S)�, �NR�C(S)�O�, �NR�C(S)�NR�, �S�S(O)2�, �S�S(O)2�O�, �S�S(O)2�NR�, �NR�O�S(O)�, �NR�O�S(O)�O�, �NR�O�S(O)�NR�, �NR�O�S(O)2�, �NR�O�S(O)2�O�, �NR�O�S(O)2�NR�, �O�NR�S(O)�, �O�NR�S(O)�O�, �O�NR�S(O)�NR�, �O�NR�S(O)2�O�, �O�NR�S(O)2�NR�, �O�NR�S(O)2�, �O�P(O)R2�, �S�P(O)R2�, �NR�P(O)R2�; wherein each R is independently hydrogen, alkyl or substituted alkyl, and the like.
As employed herein, �hydrocarbyl� embraces alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic heterocylic, substituted monocyclic heterocyclic, monocyclic aromatic, monosubstituted monocyclic aromatic, or the like.
As employed herein, �cycloalkylene� refers to divalent cyclic ring-containing groups containing in the range of about 3 up to 8 carbon atoms, and �substituted cycloalkylene� refers to cycloalkylene groups further bearing one or more substituents as set forth above.
As employed herein, �cycloalkenylene� refers to divalent, ene-functionalized (e.g., vinyl or allyl groups) cycloaliphatic groups containing in the range of about 3 up to 8 carbon atoms, and �substituted cycloalkenylene� refers to cycloalkenylene groups further bearing one or more substituents as set forth above.
As employed herein, �oxyalkylene� refers to the divalent moiety �O-alkylene-, wherein alkylene is as defined above, and �substituted oxyalkylene� refers to oxyalkylene groups further bearing one or more substituents as set forth above.
As employed herein, �oxyalkenylene� refers to the divalent, ene-functionalized moiety �O-alkenylene-, wherein alkenylene is as defined herein, and �substituted oxyalkenylene� refers to oxyalkenylene groups further bearing one or more substituents as set forth above.
As employed herein, �alkynylene� refers to divalent linear or branched chain hydrocarbyl groups having at least one carbon-carbon triple bond, and having in the range of about 2 up to 12 carbon atoms, and �substituted alkynylene� refers to alkynylene groups further bearing one or more substituents as set forth above.
Presently preferred peroxides are those having a decomposition temperature of at least about 50� C. Exemplary peroxides contemplated for use in the practice of the present invention include ketone peroxides (e.g., methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), peroxyketals (e.g., 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butyl peroxy)butane, and the like), hydroperoxides (e.g., t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and the like), dialkyl peroxides (e.g., dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3, α,α′-bis(t-butyl peroxy-m-isopropyl)benzene, and the like), diacyl peroxides (e.g., octanoyl peroxide, isobutyryl peroxide, and the like), peroxyesters (e.g., peroxydicarbonate), and the like.
Fillers that are not electrical conductors may be used in the practice of the present invention. Such fillers may be desirable to impart some other property to the composition according to the invention, such as, for example, reduced thermal expansion of the cured material, increased or reduced dielectric constant, improved toughness, increased hydrophobicity, and the like. Examples of such fillers include perfluorinated hydrocarbon polymers (i.e., TEFLON�), thermoplastic polymers, thermoplastic elastomers, mica, fused silica, glass powder, titanium dioxide, strontium oxide, and the like.
UV protectors contemplated for use in certain embodiments of the present invention include compounds which absorb incident ultraviolet (UV) radiation, thereby reducing the negative effects of such exposure on the resin or polymer system to which the protector has been added. Exemplary UV protectors include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, silicon, powdered metallic compounds, hindered amines (known in the art as �HALS�), and the like.
(a) a first component comprising a low loss, low dielectric constant, hydrocarbyl thermoplastic resin, (b) a second component which is capable of crosslinking to produce a thermoset in the presence of the first component, (c) a free radical source, (d) optionally, one or more additives, and (e) an optional diluent therefore
In a preferred embodiment, laminated sheets according to the present invention have a dielectric constant ≦4.5 nominal, electrical loss tangent ≦0.02, and a glass transition temperature of at least 80� C.
EXAMPLE 1 Several example formulations according to the invention were prepared and the performance properties thereof evaluated. The contents of the varnish designated I-2977 (90 parts cyclic olefin component: 10 parts triallyl isocyanurate) and the varnish designated I-2978 (85 parts cyclic olefin component: 15 parts triallyl isocyanurate) are summarized as set forth in Table 1, as follows:
I-2977 Formulation
I-2978 Formulation
Cyclic olefin component*
Using the above-described formulations, Glass 106 prepregs were produced using metered resin saturation and b-staging conditions of 5 minutes at 130� C. Prepregs were laminated using a lab press (120 minutes, 425� F., 300 psi), and various properties of the resulting prepregs were analyzed, as summarized in Table 2:
I-2977
I-2978
Cyclic olefin component/TAIC Ratio
% Resin Content
Decomp. Temp
CTE (x, y, z)
25/29/59
27/30/58
EXAMPLE 2 A laboratory pilot-treater equipped with an infrared ceramic oven was used to prepare I-2977-containing prepregs based on Glass 106 and Glass 1080. 64% resin content was achieved on standard 106 and 47% resin content was achieved on standard 1080. Prepregs were laminated using a lab press (120 minutes, 425� F., 300 psi) and analyzed, as summarized in Table 3.
18 Plies
[U/
(32.5 mil)
(3.4 mil)
(29.6 mil)
T260 >60
22/18/58
13/15/49
Expansion Rate Below
Expansion Rate Above
175-225 363.4
Tg (Thermoplastic, 5013
Tg (Thermoset, Cross-Linked
Expansion Rate Below Tg
50-75 114.3
Expansion Rate Above Tg
125-200 267.8
Expansion Rate Below Tg of 5013
Expansion Rate Above Tg of 5013
150-250 ~0.0
Overall Dimensional Change
Expansion Rate Below Tg of COC
Expansion Rate Above Tg of COC
In addition to the above-described evaluations, the flow properties of laboratory pilot I-2977 prepreg (106 65%, 4 plies, 340� F., 200 psi, 10 minutes) were evaluated, and can be summarized as set forth in Table 7, as follows:
2 Hole H1-Initial
2 Hole H1-Min
2 Hole H1-Max
2 Hole H2-Initial
2 Hole H2-Min
2 Hole H2-Max
EXAMPLE 3 Another batch of I-2977 (90 parts 5013 resin:10 parts triallyl isocyanurate) varnish, containing 454.0 parts of cyclic olefin component, 17.7 parts of TAIC, 1.8 parts of dicumyl peroxide, and 13.7 parts of toluene, was prepared as follows:
To 295 lbs toluene was added 159 lbs Ticona Topas 5013 resin with high shear (5700 rpm) mixing. Complete dissolution of the 5013 resin (at 35% solids) occurred in approximately 1 hour and 40 minutes. Heat-up due to shear mixing was mild (<40� C.). To the 5013 resin/toluene solution was then added 17.7 lbs of triallyl isocyanurate TAIC). 801 g of dicumyl peroxide was dissolved in 2 lbs toluene. The dicumyl peroxide/toluene solution was then added to the 5013/triallyl isocyanurate/toluene solution in the mix tank. A 10 minute high-shear mix (5700 rpm) homogenized the I-2977 varnish. Varnish viscosity (Z5) was 45 seconds.
106 glass (44 inch width) was then saturated using a production treater. 160 yards of laminate grade 106 (65% resin content) and 110 yards of laminate grade 1080 (55% resin content) was captured using the following process: Z1=225, Z2=253, Z3=279, Z4=320, Z5=320, Z6=320� F., Blower=1780/1650 cfm, Line Speed=10.5 fpm, Metering Gap=11.5, Metering Speed=1.3 fpm, Varnish Viscosity (Zahn 5)=35 seconds. Resulting solvent retention ranged from 2.8 to 3.3%.
Performance characteristics of I-2977 laminates derived from production made prepreg (106 65% and 1080 55%) laminated using a lab press (120 minutes, 425� F., 300 psi) are summarized in Table 8, as follows:
120-138/224
117-136/224
T260 <1
27/28/100
23/19/87
Performance characteristics of I-2977 laminates derived from production made prepreg (106 65% and 1080 55%) pressed on production lamination equipment (120 minutes, 425� F., 300 psi) are summarized in Table 9, as follows:
106 65%/1080 55%
115-135/224
115-137/224
27/29/110
26/24/96
7.0/6.8
106 65% and
EXAMPLE 4 I-2942 (80 parts 6017 resin: 20 parts triallyl isocyanurate, 30 phr flame retardant) and I-2947 (70 parts 6017 resin: 30 parts triallyl isocyanurate, 50 phr flame retardant) varnishes were prepared as summarized in Table 11:
I-2942 Formulation
I-2947 Formulation
Exolit OP-930
Glass 7628 and 1080 prepregs were produced using metered resin saturation and b-staging conditions involving temperature gradient drying. Prepregs were laminated using a lab press (120 minutes, 425� F., 300 psi). Selected properties of the resulting laminates are summarized in Table 12:
T260 delamination
EXAMPLE 5 I-2963 (70 parts 6017 resin: 30 parts triallyl isocyanurate, 50 phr flame retardant (equal blend of OP-930 and melamine cyanurate) varnish was prepared as summarized in Table 13:
I-2963 Formulation
Exolit OP-930**
Fyrol Melamine Cyanurate
Glass 1080 prepregs were produced using metered resin saturation and b-staging conditions of 5 minutes at 130� C. Prepregs were laminated using a lab press (120 minutes, 425� F., 300 psi).
Flame After
Burn-To-
I-2963*
All FR Layers
*Non-FR Outer-Layers
Tg (2nd Pass, DSC)
EXAMPLE 6 I-2995 (90 parts 5013 resin: 10 parts triallyl isocyanurate, 75 phr fused silica) varnish was prepared as summarized in Table 16, as follows:
I-2995 Formulation
HUF-130 Fused Silica
Glass 1080 prepregs were produced using metered resin saturation and varied b-staging conditions: 4.5, 5.0 and 6.0 minutes at 130� C. Prepregs were laminated using a lab press (120 minutes, 425� F., 300 psi). Performance properties of the resulting laminates derived from I-2995 prepreg were analyzed. Results are summarized in Table 17 as follows:
Enthalpy - Resin Only
Flow, 2 Hole Test
Dk (1 GHz)
Peel Strength AR/AS
EXAMPLE 7 I-2998 (90 parts 5013 resin: 10 parts triallyl isocyanurate, 50 phr fused silica, 0.75 phr TiO2) varnish was prepared as summarized in Table 18, which follows:
I-2998 Formulation
Glass 1080 prepregs were produced using metered resin saturation and varied b-staging conditions: 4.5, 5.0 and 6.0 minutes at 130� C. Prepregs were laminated using a lab press (120 minutes, 425� F., 300 psi). Performance properties of the resulting laminates derived from I-2998 prepreg were analyzed. Results are summarized in Table 19 as follows:
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