KR102712135B1 - Thermosetting resin composition for preparing prepreg, prepreg, and metal clad laminate - Google Patents

Abstract

The present invention relates to a thermosetting resin composition for a prepreg, a prepreg manufactured using the same, and a metal foil laminated plate manufactured using the same, and more specifically, to a thermosetting resin composition for a prepreg, a prepreg manufactured using the same, and a metal foil laminated plate manufactured using the same, which can prevent deformation due to a difference in thermal expansion coefficient in a high-temperature and high-pressure lamination process.

Description

Thermosetting resin composition for prepreg, prepreg, and metal clad laminate {THERMOSETTING RESIN COMPOSITION FOR PREPARING PREPREG, PREPREG, AND METAL CLAD LAMINATE}

The present invention relates to a thermosetting resin composition for prepreg, a prepreg manufactured using the same, and a metal foil laminated plate manufactured using the same.

Recently, with the advancement of electronic devices, high-density integration and high-density mounting of electronic components are progressing, and printed circuit boards (PCBs) are also becoming smaller, thinner, and denser.

For these printed circuit boards, metal clad laminate, which is a laminate of metal and prepreg, or copper clad laminate (CCL), which uses copper among the metals, is used.

In particular, multilayer substrates are manufactured by a method of etching metal on a metal foil laminate to create a fine circuit pattern and repeating the lamination process, and during the lamination process, pressing is performed under high-temperature conditions.

However, under these high temperature and high pressure process conditions, residual stress may occur due to differences in thermal expansion coefficients between materials, which may lead to warping of the substrate.

Therefore, research is needed on a metal laminate that can prevent deformation due to differences in thermal expansion coefficients and thereby increase reliability.

The present specification provides a thermosetting resin composition for a prepreg, which can prevent deformation due to a difference in thermal expansion coefficient in a high-temperature and high-pressure lamination process, a prepreg manufactured using the same, and a metal foil laminated plate manufactured using the same.

According to one aspect of the present invention, a thermosetting resin composition for a prepreg is provided, comprising: a binder resin; a filler; and an oligomer represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

R1 and R2 are each independently, identically or differently, hydrogen, alkyl having 1 to 3 carbon atoms, phenyl, or phenol;

n1 and n2 are the repetition numbers of each repeating unit, each independently, identically or differently, from 1 to 15.

At this time, in the oligomer represented by the chemical formula 1, it may be preferable that n1 is about 60 to about 99.9% relative to the value of n1+n2, and n2 is about 0.1 to about 40% relative to the value of n1+n2.

And, the oligomer represented by the chemical formula 1 may have a weight average molecular weight value of about 500 to about 3,000, and it may be more preferable to have a weight average molecular weight value of about 1,000 to about 3,000.

And, the oligomer represented by the chemical formula 1 may have a softening point value of about 90 to about 130° C. measured according to the ASTM D 1525 standard due to the characteristics of the molecular structure.

According to one embodiment of the invention, the binder resin may include at least one selected from the group consisting of polyphenylene ether resin, cyanate ester resin, bismaleimide resin, butadiene resin, phenoxy resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, and polyetheretherketone resin.

In addition, the filler may include at least one selected from the group consisting of inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles.

At this time, the filler may be included in an amount of about 10 to about 100 parts by weight, preferably about 50 to about 90 parts by weight, relative to 100 parts by weight of the binder resin.

And, the oligomer represented by the chemical formula 1 may be included in an amount of about 1 to about 50 parts by weight, preferably about 10 to about 30 parts by weight, with respect to 100 parts by weight of the binder resin.

According to another embodiment of the invention, the thermosetting resin composition for prepreg may further include one or more additives selected from the group consisting of a curing agent, a flame retardant, a UV shielding agent, a leveling agent, a thickener, a pigment, a dispersant, a plasticizer, and an antioxidant.

Meanwhile, according to another aspect of the present invention, a prepreg is provided, which includes a fiber substrate impregnated with the thermosetting resin composition for prepreg described above.

The type of the above fiber substrate is not particularly limited, but at least one of organic fiber and glass fiber may be used.

Meanwhile, according to another aspect of the present invention, a metal-clad laminate is provided, comprising: a cured resin layer; and a metal layer formed on at least one surface of the cured resin layer; wherein the cured resin layer comprises a cured product of the thermosetting resin composition for prepreg.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention.

Singular expressions include plural expressions unless the context clearly indicates otherwise.

In this specification, the terms “comprise,” “include,” or “have” are intended to describe a feature, number, step, component, or combination thereof implemented, but do not exclude the possibility of one or more other features, numbers, steps, components, combinations, or additions thereof.

Additionally, in this specification, when each layer or element is referred to as being formed “on” or “over” each of the layers or elements, it means that each layer or element is formed directly on each of the layers or elements, or that other layers or elements may be additionally formed between each of the layers, on the object, or on the substrate.

The present invention may have various modifications and may take various forms, and specific embodiments are exemplified and described in detail below. However, this does not limit the present invention to a specific disclosed form, but should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, a thermosetting resin composition for a prepreg is provided, comprising: a binder resin; a filler; and an oligomer represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

R1 and R2 are each independently, identically or differently, hydrogen, alkyl having 1 to 3 carbon atoms, phenyl, or phenol;

n1 and n2 are the repetition numbers of each repeating unit, each independently, identically or differently, from 1 to 15.

As described above, when manufacturing a multilayer circuit-based substrate using prepreg, a high temperature and high pressure pressing process is required, and at this time, warping of the substrate may occur depending on the difference in thermal expansion coefficient between each material.

In order to prevent material deformation under high temperature conditions such as the above, a method of increasing the content of filler is generally used.

However, as the content of filler increases, there is a problem that the flowability of the resin within the prepreg decreases, and when forming a metal pattern, a problem that the filling property of the pattern decreases may occur.

The inventors of the present invention have discovered that when the oligomer represented by the above-described chemical formula 1 is used as a thermosetting resin composition for a prepreg, the oligomer can reduce the curing density of the resin composition, thereby alleviating internal stress due to a difference in thermal expansion coefficient in a high-temperature and high-pressure pressing process in the manufactured prepreg, thereby alleviating deformation, while hardly causing a deterioration in other physical properties required for a metal-clad laminate, such as a dielectric constant, and thus completing the present invention.

The oligomer represented by the above chemical formula 1 is a copolymer oligomer that includes both repeating units derived from a styrene monomer and repeating units derived from indene, the terminal of which is terminated with hydrogen, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a phenol group, wherein n1 is the repeating number of the repeating unit derived from the indene monomer, and n2 is the repeating number of the repeating unit derived from the styrene monomer.

The oligomer represented by the above chemical formula 1, as described above, includes a cyclic alkyl group connected to a benzene ring and a cyclic heteroalkyl group connected to the benzene ring, and thus has a rigid chemical bonding structure. Due to this rigid chemical structure, when the prepreg is cured, the curing density of the cured product can be somewhat reduced, and thus, internal stress that may occur due to a difference in the thermal expansion coefficient of each material in a high-temperature pressing process can be alleviated.

At this time, in the oligomer represented by the chemical formula 1, it may be preferable that n1 is about 60 to about 99.9% relative to the value of n1+n2, and n2 is about 0.1 to about 40% relative to the value of n1+n2.

The value of n1+n2 refers to the total number of repetitions of each repeating unit present in the above-described oligomer molecule, and the ratio of n1 and n2 to this refers to the molar ratio of each monomer-derived repeating unit present in the oligomer molecule.

According to this ratio, the ratio of n1, that is, the ratio of the repeating unit derived from the indene monomer in the oligomer molecule, may be from about 60 to about 99.9 mol%, more preferably, from about 80 to about 99.9 mol%, or from about 90 to about 99.5 mol%. When the ratio of the repeating unit derived from the indene monomer is too low, the rigidity of the oligomer molecule may be reduced, and thus, it may be difficult to obtain the effects of the present invention described above, and a problem of weakening the bonding between the prepreg and the metal may occur.

And, the ratio of n2, that is, the ratio of repeating units derived from styrene monomers within the oligomer molecule, may be from about 0.1 to about 40 mol%, and may be preferably from about 0.1 to 20 mol%, or from about 0.5 to 10 mol%, in terms of controlling the rigidity and viscosity of the oligomer molecule.

And, the oligomer represented by the chemical formula 1 may have a weight average molecular weight value of about 500 to about 3,000, more preferably, a weight average molecular weight value of about 1,000 to about 3,000, by including the repeating units derived from each of the above-described monomers in a ratio within the above range.

When the weight average molecular weight value is too small, the size of the oligomer molecules is too small, which may not be suitable for the purpose of slightly reducing the curing density of the cured product when the prepreg is cured, and thus it may be difficult to obtain the effects of the present invention described above. When the weight average molecular weight value is too large, the rigidity of the molecules becomes too high, and when the prepreg is cured, the curing density of the cured product becomes too low, which may cause a problem in that the mechanical properties of the metal-clad laminate being manufactured deteriorate.

These weight-average molecular weight values may be calculated according to the calibration curve of polystyrene standards having molecular weights of 1,000, 2,000, and 5,000, while supplying 200 μL of the target sample at a concentration of 10 mg/10 mL at a flow rate of 1 mL/min in the presence of a 1,2,4-trichlorobenzene solvent at 160°C using gel permeation chromatography (GPC).

And, the oligomer represented by the above chemical formula 1 may have a softening point value of about 90 to about 130° C. as measured according to the ASTM D 1525 standard due to the characteristics of the molecular structure. Since the softening point value of the oligomer is within the above-described range, it can be well mixed into the binder during prepreg manufacturing and curing in the high-temperature pressing process, and can appropriately reduce the curing density of the binder, thereby reducing the difference in coefficient of thermal expansion (CTE) of each material, and effectively alleviating internal stress.

According to one embodiment of the invention, the binder resin may be a binder resin generally known in the technical field to which the present invention pertains, and specifically, for example, polyphenylene ether resin, cyanate ester resin, bismaleimide resin, butadiene resin, phenoxy resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, and polyetheretherketone resin may be used alone or in combination of one or more thereof.

More specifically, the binder resin may include polyphenylene ether resin (a), bismaleimide resin (b), cyanate ester resin (c), and/or styrene-butadiene resin (d), and since the resins have better compatibility with the organic-inorganic composite filler, they can further improve moisture absorption and heat resistance and processability while lowering dielectric properties.

The above phenylene ether resin (a) may include a modified phenylene ether oligomer or modified poly(phenylene ether) functionalized at both terminals with ethylenically unsaturated groups. The two ethylenically unsaturated groups functionalized at both terminals of the (a) component may be the same or different.

Examples of the ethylenically unsaturated group include an alkenyl group such as an ethenyl group, an allyl group, a methallyl group, a propenyl group, a butenyl group, a hexenyl group, and an octenyl group; a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group; an acryl group, a methacryl group; or an alkenylaryl group such as a vinylbenzyl group and a vinylnaphthyl group.

The method for producing the above component (a) is not particularly limited, but for example, one functionalized with a vinylbenzyl group can be produced by dissolving a difunctional phenylene ether oligomer and vinylbenzene chloride in a solvent, adding a base to react under heating and stirring, and then solidifying the resin.

The number average molecular weight of the above component (a) may be in the range of about 500 to about 3,000, or about 1,000 to about 2,500, as converted to polystyrene by the GPC method. If the number average molecular weight of the above component (a) is less than about 500 g/mol, a problem may occur in which a prepreg formed using the above resin composition does not adhere well, and if it exceeds about 3,000 g/mol, solubility in a solvent may decrease.

As the above bismaleimide resin (b) and cyanate ester resin (c), any resin well known in the technical field to which the present invention belongs can be used without any particular limitation.

For example, the bismaleimide resin (b) may be a diphenylmethane-type bismaleimide such as 4,4'-diphenylmethane bismaleimide, an oligomer of phenylmethane maleimide, a phenylene-type bismaleimide such as m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, It may be at least one compound selected from the group consisting of 1,6-bismaleimide-(2,2,4-trimethyl)hexane.

In addition, for example, the cyanate ester resin (c) may be at least one compound selected from the group consisting of novolac-type cyanate resin, dicyclopentadiene-type cyanate resin, bisphenol-type cyanate resin, and some triazinated prepolymers thereof.

The above styrene-butadiene resin (d) is a copolymer resin of styrene and butadiene, is liquid at room temperature, and may have a styrene content of about 5 to about 50%. In addition, the styrene-butadiene resin (d) may have a glass transition temperature (Tg) of about -35°C to about 0°C or about -30°C to about -5°C; and a number average molecular weight of about 1,000 to about 50,000 or about 2,000 to about 10,000.

In addition, the filler may include at least one selected from the group consisting of inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles.

At this time, the inorganic fine particles may specifically be silicon-based fine particles such as natural silica, fused silica, amorphous silica, crystalline silica, or mineral or salt fine particles such as boehmite, alumina, talc, glass, calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, titanium oxide, antimony oxide, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica, and the like, and these may be used alone or in combination of two or more.

And, the organic particulate matter may specifically be, for example, a fluorine-based organic particulate matter such as a polytetrafluoroethylene powder, a tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), an ethylene-chlorotrifluoroethylene copolymer (PCTFE), and polyfluorovinylidene (PVDF), and these may be used alone or in combination of two or more thereof.

In addition, the above-described organic-inorganic composite fine particles may be organic-inorganic composite fine particles having a core-shell structure, which include the above-described inorganic fine particles or organic fine particles as a core component and are surface-treated with a silane coupling agent to form a shell.

At this time, the filler may be included in an amount of about 10 to about 100 parts by weight, preferably about 50 to about 90 parts by weight, relative to 100 parts by weight of the binder resin. If the filler is used in an excessively small amount, the thermal expansion coefficient of the prepreg increases, which may result in a problem of warping due to heat after the substrate is manufactured and the semiconductor chip is mounted, and if the filler is used in an excessive amount, the flowability of the thermosetting resin composition for the prepreg may be reduced.

However, according to one aspect of the present invention, since the difference in thermal expansion coefficients of each prepreg material can be effectively reduced by the above-described oligomer, the filler can be used in a smaller amount than that generally used in the field to which the present invention pertains, and thus, there is an advantage in that the flowability of the thermosetting resin composition for prepreg can be further improved.

And, the oligomer represented by the chemical formula 1 may be included in an amount of about 1 to about 50 parts by weight, preferably about 10 to about 30 parts by weight, based on 100 parts by weight of the binder resin. If the amount of the oligomer represented by the chemical formula 1 is too small, it may not be sufficient to implement the above-described effect, and if the amount of the oligomer represented by the chemical formula 1 is too large, the curing of the binder may be delayed and the curing density may be too greatly reduced, which may cause a problem in that the mechanical properties of the prepreg and substrate manufactured later deteriorate.

According to another embodiment of the invention, the thermosetting resin composition for prepreg may further include one or more additives selected from the group consisting of a curing agent, a flame retardant, a UV shielding agent, a leveling agent, a thickener, a pigment, a dispersant, a plasticizer, and an antioxidant.

As the curing agent, any conventional curing agent known in the technical field to which the present invention pertains can be used without limitation, and specifically, for example, at least one curing agent selected from an amide-based curing agent, a polyamine-based curing agent, an acid anhydride curing agent, a phenol novolac-based curing agent, a polymercaptan curing agent, a tertiary amine curing agent, an imidazole curing agent, and a metal coordination catalyst can be used. Specifically, the metal coordination catalyst can be cobalt (II) acetate, which can promote a triazine bond of a cyanate ester that can be included in the binder resin.

In the resin composition, the content of the curing agent may be 0.1 to 10 wt%, 0.2 to 8 wt%, or 0.5 to 5 wt%, based on the total weight of the resin composition.

As the flame retardant, a conventional flame retardant known in the technical field to which the present invention belongs can be used without any particular limitation, and examples thereof include halogen flame retardants containing bromine or chlorine; phosphorus flame retardants such as triphenyl phosphate, triquecyl phosphate, trisdichloropropyl phosphate, and phosphazene; antimony flame retardants such as antimony trioxide; and inorganic flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide.

In the resin composition, the content of the flame retardant may be 0.1 to 10 wt%, 0.2 to 8 wt%, or 0.5 to 5 wt%, based on the total weight of the resin composition. If the content of the flame retardant is less than 0.1 wt%, flame resistance may not be achieved, and if it exceeds 10 wt%, electrical properties may deteriorate.

Meanwhile, according to another aspect of the present invention, a prepreg is provided, which includes a fiber substrate impregnated with the thermosetting resin composition for prepreg described above.

The type of the above fiber substrate is not particularly limited, but at least one of organic fiber and glass fiber may be used.

As the organic fibers mentioned above, a synthetic fiber substrate composed of a woven or nonwoven fabric mainly composed of polyamide-based resin fibers such as aramid fibers, polyamide resin fibers, and aromatic polyamide resin fibers, polyester-based resin fibers such as polyester resin fibers, aromatic polyester resin fibers, and wholly aromatic polyester resin fibers, polyimide resin fibers, and fluororesin fibers, a paper substrate mainly composed of kraft paper, cotton lint paper, and mixed paper of linter and kraft pulp, etc. can be used.

The glass fiber can improve the strength of the prepreg, thereby lowering the absorption rate, and also lowering the thermal expansion coefficient. The glass fiber substrate used in the present invention can be selected from glass substrates used for various printed circuit board materials. Examples thereof include, but are not limited to, glass fibers such as E glass, D glass, S glass, and NE glass. The glass substrate material can be selected according to the intended use or performance as needed. The form of the glass substrate is typically a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, or a surfacing mat. The thickness of the glass substrate is not particularly limited, but can be used in a range of about 0.01 to 0.3 mm, or the like. Among the materials, a glass fiber material is more preferable in terms of strength and water absorption characteristics.

The method for manufacturing the above prepreg is not particularly limited, and a manufacturing method generally known in the technical field to which the present invention belongs can be followed.

Prepreg specifically refers to a sheet-shaped material obtained by coating or impregnating the above-described fiber substrate with the above-described thermosetting resin composition for prepreg, and then curing it to the B-stage (semi-cured state) by heating.

At this time, the heating temperature and time are not particularly limited, and for example, the heating temperature may be about 20 to 200°C or about 70 to about 170°C, and the heating time may be in the range of about 1 to about 10 minutes.

In addition to this method, the prepreg may also be manufactured by a hot melt method, a solvent method, or the like known in the art pertaining to the present invention.

The solvent method is a method of dissolving a thermosetting resin composition for prepreg in an organic solvent, impregnating a fiber substrate with the formed varnish, and then drying it. Examples of the method for impregnating a fiber substrate with the thermosetting resin composition for prepreg include a method of immersing a fiber substrate in varnish, a method of applying varnish to a substrate by various coaters, a method of spraying varnish onto a substrate, etc. At this time, when the fiber substrate is immersed in a resin varnish, it is preferable because the impregnation property of the resin composition for the fiber substrate can be improved.

When preparing the above varnish, examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and tetrahydrofuran. The above organic solvents may be used alone or in combination of two or more.

In addition, in the case of the hot melt method, the resin composition may be coated on a release paper having excellent peelability without dissolving it in an organic solvent, and then laminated on a sheet-shaped fiber substrate or directly coated using a die coater. In addition, the adhesive film made of the resin composition laminated on a support may be continuously thermally laminated from both sides of a sheet-shaped reinforcing substrate under heating and pressurizing conditions.

Meanwhile, according to another aspect of the present invention, a metal-clad laminate is provided, comprising: a cured resin layer; and a metal layer formed on at least one surface of the cured resin layer; wherein the cured resin layer comprises a cured product of the thermosetting resin composition for prepreg.

For example, the metal foil laminated plate can be manufactured by laminating one or more sheets of the prepreg of the above-described embodiment, overlapping a metal foil on one or both sides thereof as necessary, and then heating and pressing.

The heating and pressurizing conditions during the manufacture of the above laminated plate are not particularly limited, but may be applied at a temperature range of about 140 to about 220° C. and a pressure of about 70 to about 800 psi. The above temperature and pressure ranges may be advantageous for improving interlayer adhesion, heat resistance, reliability, etc. of the laminated plate.

In addition, as a device for heating and pressurizing when manufacturing the laminated plate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used, but the laminated plate of the above embodiment is not limited thereto.

In addition, the metal foil used to form the above metal layer is for forming a pattern of the substrate and is not particularly limited, but may be made of one or more metals from among copper, aluminum, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, and lead-tin alloy.

In addition, the metal foil laminated plate can also be manufactured by, for example, a method of manufacturing a resin composition that has not been processed into a prepreg into a varnish, applying it to a metal foil, and then drying it.

The varnish for producing the above resin-attached metal foil contains a solvent, similar to the varnish composition for producing the above-described prepreg, but may further contain a curing agent, a curing catalyst, etc.

The metal foil mentioned above can be made of a common metal or alloy well known in the technical field to which the present invention belongs without limitation. At this time, the metal foil may be copper foil, and examples of usable copper foil include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN, etc.

The above copper foil includes all copper foils manufactured by rolling and electrolytic methods. Here, the copper foil may be treated with an anti-rust treatment to prevent the surface from being oxidized and corroded.

The metal foil may have a predetermined surface roughness (Rz) formed on one surface of the metal foil that comes into contact with the cured resin layer of the resin composition. At this time, the surface roughness (Rz) is not particularly limited, but may be in the range of about 0.6 to about 3.0 ㎛, for example.

In addition, the thickness of the metal foil is not particularly limited, but may be less than about 5 ㎛ or about 1 to about 3 ㎛ in consideration of the thickness and mechanical properties of the final product.

The thermosetting resin composition for prepreg of the present invention can prevent deformation due to a difference in thermal expansion coefficient in a high-temperature and high-pressure lamination process, thereby providing a highly reliable substrate.

Hereinafter, the operation and effect of the invention will be described in more detail through specific examples of the invention. However, these examples are presented only as examples of the invention, and the scope of the invention's rights is not determined thereby.

<Example>

Preparation of thermosetting resin composition for prepreg

A thermosetting resin composition for prepreg was prepared by mixing a binder resin, a filler, an oligomer, and an additive according to the composition described in Table 1 below and stirring for about 4 hours.

division Comparative Example 1
(weight) Comparative Example 2
(weight) Example 1
(weight) Example 2
(weight) bookbinder OPE-2st-1200 22 25 22.5 20 ULL-950s 55 55 49.5 44 BMI-5100 20 20 18 16 KG3015P GMA 3 - - - Inden
Oligomer IP-100 - - 10 20 Additives Co(acac)2
(cobalt catalyst) 0.035 0.035 0.315 0.028 SB-141
(pigment) 1 1 1 1 Filler SC2050HNJ 68 68 68 68 AC4130Y 7 7 7 7

* OPE-2st-1200: Oligo Phenylnene Ether; MGC company

* ULL-950s: Cyanate ester; LONZA company

* BMI-5100: Bismaleimide resin; DAIWA

* KG3015P GMA: Acrylic rubber, NEGAMI

* IP - 100: Copolymer oligomer (Nippon Steel & Sumikin Chemical)

* SC2050MTO: Phenylaminosilane-treated slurry type micro silica, average particle size 0.5 ㎛; Admantechs

* AC4130Y: Nano silica of slurry type treated with methacrylic silane, average particle size 50 nm

Manufacturing of prepreg and copper-clad laminates

The resin compositions of the examples and comparative examples were impregnated into glass fibers (13 ㎛ thick, manufactured by Nittobo, 1017, NE-glass) surface-treated with vinyl silane, and then dried at a temperature of about 130 to about 160°C for about 3 to about 10 minutes to produce a prepreg having a thickness of about 30 ㎛.

Two sheets of the above prepreg were laminated and copper foil (12 ㎛ thick, manufactured by Mitsui) was pressed on both sides to manufacture a copper-clad laminate.

evaluation

In the manufactured copper-clad laminate, the copper foil was removed by etching, and physical properties were measured for the laminate from which the copper foil was removed.

Measurement of dielectric constant and dielectric loss factor

The dielectric constant and dielectric loss factor at a frequency of 1 GHz were measured and evaluated using a dielectric constant measuring device (RF Impedence, Agilent) by the SPDR (Split post dielectric resonance) method.

Measurement of glass transition temperature values

For the laminates manufactured in each example and comparative example, the glass transition temperature range was measured according to the standard in expansion mode using a TMA (Thermomechanical analysis, TA) device. The specific measurement conditions are as follows.

Film/fiber probe type; Preload force: 0.1 N; Length: 16mm

<method log>

Equilibrate at 30℃; Ramp 10℃?/min. to 140℃?; Isothermal 1min.; Ramp 10℃?/min. to 30℃?; Isothermal 1 min.; Ramp 10℃?/min. to 260℃?; Isothermal 1min.; Ramp 10℃?/min. to 30℃?

Adhesion measurement

The adhesion between the prepreg and the copper foil was measured using a Texture Analyzer (AX plus, Stable Micro System).

Measurement of high temperature shrinkage phenomenon

For the laminates manufactured in each example and comparative example, the shrinkage phenomenon of the laminates was measured in the expansion mode using a TMA (Thermomechanical analysis, TA) device in a range of about 10℃ or higher from the glass transition temperature according to the standard.

The specific measurement conditions are as follows.

Film/fiber probe type; Preload force: 0.1 N; Length: 16mm

<method log>

Equilibrate at 30℃; Ramp 10℃/min. to 140℃; Isothermal 1min.; Ramp 10℃/min. to 30℃; Isothermal 1 min.; Ramp 10℃/min. to 260℃; Isothermal 1min.; Ramp 10℃/min. to 30℃

The measurement results are summarized in Table 2 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 dielectric constant
(Dk @ 1 GHz) 3.52 3.44~3.48 3.46 3.46 Genetic loss rate
(Df @ 1 GHz) 0.003 0.003 0.003 0.003 Glass transition temperature
(℃) 250 254 234 219 Adhesion
(kgf/cm) 0.73 0.7 0.76 0.76 High temperature shrinkage
(unit:%)
Temperature range:
Tg ~ +10 ℃ -0.013 -0.006 -0.002 0.001

Referring to Table 2 above, it can be seen that the thermosetting resin composition for prepreg according to an embodiment of the present invention has a glass transition temperature value that is lowered by about 10°C or more, while there is no significant difference in electrical properties, such as relative permittivity or dielectric loss factor, compared to the comparative example, and it can be confirmed that the adhesion between the prepreg and the copper foil is formed very strongly, while the shrinkage rate is significantly reduced at a high temperature of about Tg+ 10°C. In particular, in the case of the comparative example, the shrinkage phenomenon continued to accelerate even in a high temperature region exceeding the measured temperature range, whereas in the case of the example of the present application, almost no shrinkage phenomenon occurred even in a high temperature region exceeding the measured temperature range.

Therefore, it is expected that the prepreg manufactured using the thermosetting resin composition for prepreg according to one embodiment of the present invention will have less internal stress due to the difference in thermal expansion coefficient in a high-temperature and high-pressure lamination process compared to the conventional one, and it is thought that it can effectively alleviate deformation of the substrate due to residual stress, etc.

Claims (12)

A thermosetting resin composition for a prepreg, comprising a binder resin comprising a polyphenylene ether resin, a cyanate ester resin, and a bismaleimide resin; a filler; and an oligomer represented by the following chemical formula 1:
[Chemical Formula 1]

In the above chemical formula 1,
R1 and R2 are each independently, identically or differently, hydrogen, alkyl having 1 to 3 carbon atoms, phenyl, or phenol;
n1 and n2 are the repetition numbers of each repeating unit, each independently, identically or differently, from 1 to 15.
In the first paragraph,
The above n1 is 60 to 99.9% of the value of n1+n2,
The above n2 is 0.1 to 40% of the value of n1+n2.
Thermosetting resin composition for prepreg.
In the first paragraph,
A thermosetting resin composition for a prepreg, wherein the oligomer represented by the above chemical formula 1 has a weight average molecular weight value of 500 to 3,000.
In the first paragraph,
A thermosetting resin composition for a prepreg, wherein the oligomer represented by the above chemical formula 1 has a softening point value of 90 to 130°C as measured according to the ASTM D 1525 standard.
delete In the first paragraph,
A thermosetting resin composition for a prepreg, wherein the filler comprises at least one selected from the group consisting of inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles.
In the first paragraph,
A thermosetting resin composition for prepreg, wherein the filler is contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the binder resin.
In the first paragraph,
A thermosetting resin composition for a prepreg, wherein the oligomer represented by the chemical formula 1 is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the binder resin.
In the first paragraph,
A thermosetting resin composition for a prepreg, further comprising one or more additives selected from the group consisting of a curing agent, a flame retardant, a UV shielding agent, a leveling agent, a thickener, a pigment, a dispersing agent, a plasticizer, and an antioxidant.
A prepreg comprising a fiber substrate impregnated with a thermosetting resin composition for prepreg according to claim 1.
In Article 10,
The above fiber substrate is a prepreg, which is at least one of organic fiber and glass fiber.
a cured resin layer; and
Comprising a metal layer formed on at least one surface of the cured resin layer;
The above cured resin layer comprises a cured product of the thermosetting resin composition for prepreg according to claim 1;
Metal foil laminate.