CN109504037B - Resin composition, and prepreg and laminated board prepared from same - Google Patents
Resin composition, and prepreg and laminated board prepared from same Download PDFInfo
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- CN109504037B CN109504037B CN201811395824.8A CN201811395824A CN109504037B CN 109504037 B CN109504037 B CN 109504037B CN 201811395824 A CN201811395824 A CN 201811395824A CN 109504037 B CN109504037 B CN 109504037B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- 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
- B32B5/02—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 structural features of a fibrous or filamentary layer
- B32B5/026—Knitted fabric
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- 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
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- 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
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- 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
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
Abstract
The invention discloses a resin composition, which comprises the following components in parts by mass: hydantoin epoxy resin: 5-85 parts by mass; silicone resin: 15-95 parts by mass; siloxane oligomers and/or alicyclic/hydrogenated anhydrides: 1-55 parts by mass; polymerization inhibitor: 0.01 to 10 parts by mass; filling: 10-260 parts by mass; coupling and/or dispersing agents: 0.01-5 parts by mass, and the sum of the hydantoin epoxy resin and the silicone resin is 100 parts by mass. Compared with the prior art, the siloxane oligomer and/or alicyclic/hydrogenated acid anhydride and the polymerization inhibitor are added into the hydantoin epoxy resin and the silicone resin, so that the prepared resin composition has the advantages of good yellowing resistance, low water absorption and thermal expansion coefficient, excellent heat resistance and the like.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition and a prepreg and a laminated board prepared from the resin composition.
Background
In recent years, LEDs with short wavelengths such as blue light and white light have been rapidly developed, and therefore, copper-clad plates with excellent ultraviolet discoloration resistance, heat discoloration resistance and high light reflectivity have also been rapidly developed and applied in the field of LED applications. It has become a product meeting the special performance requirements in copper-clad plates. In addition, some terminal clients feed back the bottleneck that packaging and heat dissipation are difficult, and therefore, the ultraviolet discoloration resistance, yellowing resistance and heat conduction capability are about to be the technical research hotspots and important performance indexes of the copper-clad plate for the packaging carrier plate.
In the aspect of the performance requirements of the LED on the white copper-clad plate, besides the general performance requirements of the conventional CCL, the LED has some special performance requirements: (1) high reflectivity of the board, namely, the white substrate is required to be in the wavelength region of blue light and near ultraviolet light in order to ensure that the LED has higher luminous efficiency, namely, the visible short wavelength region is 380nm-420nm, the board surface does not change color when the high heat radiation is carried out, the board surface does not change color when the ultraviolet light irradiates for a long time, and the like; (2) resistance to ultraviolet discoloration and resistance to thermal discoloration: the white substrate is required to have not only high reflectance but also high reflectance for a long time; (3) in addition to the above requirements, the printed circuit board for mounting the LED is required to maintain good adhesion with the metal copper foil.
The route of the prior art is as follows: (1) the technical route of the lipid cyclization resin, such as patents CN101218285A, CN 103641998A and CN 103459493A, has the characteristics of general yellowing resistance, but has the defects of low viscosity of the resin, soft prepared prepreg, low glass transition temperature, high water absorption rate, high thermal expansion coefficient and the like; (2) the technical route of the silicone resin has two types according to reaction mechanisms, wherein one type is a hydrosilylation reaction, such as patent CN 106467668A and JP 2011-; the other technical route is polycondensation reaction, the polycondensation type silicon resin is the resin with the largest dosage at present, for example, the technical route of CN 105778505A has the characteristics of yellowing resistance, excellent weather resistance and low water absorption rate, and has the defects that small molecular substances are released in the curing reaction process, so that the problems of bubbles between a base material and an adhesive layer, poor heat resistance, low adhesive force between the base material and metal (particularly low adhesive strength between the base material and metal copper foil) and the like are caused.
In view of the above, there is a need for a resin composition which has excellent yellowing resistance, weather resistance, peel strength, heat resistance, low water absorption rate, low thermal expansion coefficient, and the like, and can be used for preparing prepregs (prepregs) and laminates.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a resin composition having excellent yellowing resistance, weather resistance, peel strength, heat resistance, low water absorption, low thermal expansion coefficient, and the like.
The resin composition comprises the following components in parts by mass:
hydantoin epoxy resin: 5-85 parts by mass;
silicone resin: 15-95 parts by mass;
siloxane oligomer containing amino or hydroxyl groups: 1-55 parts by mass;
polymerization inhibitor hexynol: 0.01 to 10 parts by mass;
filling: 10-260 parts by mass;
coupling and/or dispersing agents: 0.01-5 parts by mass;
the total of the hydantoin epoxy resin and the silicone resin is 100 parts by mass.
As a further improvement of the invention, the hydantoin epoxy resin has the following structure:
wherein R is1And R2Is a hydrogen atom or a methyl or ethyl group, R1And R2Same or different, n is an integer of 1 to 6。
As a further improvement of the present invention, the silicone resin is a condensation type silicone resin.
As a further improvement of the present invention, the silicone resin is at least one of methyl silicone resin, phenyl silicone resin and methyl phenyl silicone resin.
As a further improvement of the invention, the filler is any one of zinc oxide, alumina, titanium dioxide, silica, montmorillonite and calcium carbonate or any combination thereof.
As a further improvement of the present invention, the coupling agent is a silane coupling agent or a titanate coupling agent; the dispersing agent is a high molecular polymer with an acid value of 10-260 mg KOH/g.
Correspondingly, the invention also provides a prepreg, which is prepared by adding a solvent into the resin composition to dissolve the resin composition to prepare a glue solution, dipping the reinforcing material into the glue solution, and heating and drying the dipped reinforcing material.
Correspondingly, the invention also provides a laminated board, wherein the two sides of at least one prepreg are covered with release films, and the laminated board is obtained by hot press forming.
Compared with the prior art, the invention has the following advantages because the siloxane oligomer and/or the alicyclic/hydrogenated anhydride and the polymerization inhibitor are added into the hydantoin epoxy resin and the silicone resin:
(1) the problem of sticking of the prepreg (PP) is solved;
(2) the problems of low adhesive force between the substrate and the copper foil and poor heat resistance are solved;
(3) has the advantages of good yellowing resistance, low water absorption and thermal expansion coefficient, excellent heat resistance and the like.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention. Variations in reaction conditions, amounts of reactants or starting materials, which may be made by one of ordinary skill in the art in light of these examples, are within the scope of the invention.
In one embodiment of the present invention, a resin composition comprises the following components in parts by mass:
hydantoin epoxy resin: 5-85 parts by mass;
silicone resin: 15-95 parts by mass;
siloxane oligomers and/or alicyclic/hydrogenated anhydrides: 1-55 parts by mass;
polymerization inhibitor: 0.01 to 10 parts by mass;
filling: 10-260 parts by mass;
coupling and/or dispersing agents: 0.01 to 5 parts by mass.
Wherein the total of the hydantoin epoxy resin and the silicone resin is 100 parts by mass.
Further, the hydantoin epoxy has the following structure:
wherein R is1And R2Is a hydrogen atom or a methyl or ethyl group, R1And R2The same or different, and n is an integer of 1 to 6.
The content of the hydantoin epoxy resin is 5 to 85 parts by mass, preferably 10 to 85 parts by mass, based on 100 parts by mass of the hydantoin epoxy resin and the polycondensation silicone in total.
Further, the silicone resin is a condensation type silicone resin. Preferably at least one of methyl silicone resin, phenyl silicone resin and methyl phenyl silicone resin.
The content of the polycondensation silicone resin is 15 to 95 parts by mass, preferably 20 to 90 parts by mass, per 100 parts by mass of the sum of the hydantoin epoxy resin and the polycondensation silicone.
Further, the siloxane oligomer and/or the alicyclic/hydrogenated acid anhydride contain at least one group selected from an amino group, a hydroxyl group, an epoxy group, and a carboxyl group.
The content of the siloxane oligomer and/or the alicyclic/hydrogenated acid anhydride is 1 to 55 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the total of the hydantoin epoxy resin and the silicone resin.
Further, the polymerization inhibitor is at least one of fatty acid, phosphate, hexynol and benzotriazole.
The content of the polymerization inhibitor is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the sum of the hydantoin epoxy resin and the silicone resin.
Further, the filler is any one or any combination of zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, montmorillonite and calcium carbonate, and the titanium dioxide, the aluminum oxide and the silicon dioxide are preferred.
The content of the filler is 10 to 260 parts by mass relative to 100 parts by mass of the total of the hydantoin epoxy resin and the silicone resin.
Further, the coupling agent is a silane coupling agent or a titanate coupling agent; the dispersant is a high molecular polymer with an acid value of 10-260 mg KOH/g, such as BYK903 and BYK110, and the acid value is preferably 20-235 KOH/g.
The content of the coupling agent/dispersant is 0.01-5 parts by mass relative to 100 parts by mass of the total of the hydantoin epoxy resin and the silicone resin.
The invention also provides a prepreg prepared by adopting the resin composition, which comprises the following preparation steps:
dissolving the resin composition with a solvent to obtain a solution with a solid content of 60-75%, uniformly stirring, and curing to obtain a resin composition glue solution;
and (3) soaking the reinforcing material in the resin composition glue solution, and then baking the soaked reinforcing material at the temperature of 80-180 ℃ for 1-10min to dry to obtain the prepreg.
Among them, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is particularly preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. In addition, in order to improve the interfacial bonding between the resin and the glass cloth, the glass cloth generally needs to be chemically treated, mainly by a coupling agent such as epoxy silane, amino silane, etc.
The solvent is selected from one or the combination of any of acetone, butanone, toluene, xylene, ethanol, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether.
The invention also provides a laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board.
The number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited.
The laminated board can be prepared by laminating in a vacuum press under the pressure condition of 5-35 kg/cm2, the laminating temperature of 180-210 ℃ and the laminating time of 70-200 min.
In order to better illustrate the present invention, specific examples are provided below, which are further described below, and the following are specific synthetic examples of resin compositions, prepregs and laminates:
the first embodiment is as follows:
50g of hydantoin epoxy resin (MHR-154B, manufactured by Takebei tin-Etherchemical Co., Ltd.), 50g of phenyl silicone resin, 10g of amino-containing siloxane oligomer (A1100, mechanical performance materials Inc.), 0.2g of hexynol, 0.10g of dispersant (BYK-110), 100g of rutile titanium dioxide and a proper amount of acetone solvent are added into a 500ml beaker, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 65 percent. And selecting 300 (warp) × 280 (weft) cm flat and smooth E-glass fiber cloth 2116, uniformly coating the glue solution, and baking in an oven at 110 ℃ for 10min to obtain the semi-cured bonding sheet with the resin content of 50%. And overlapping 8 bonding sheets with burrs cut off, attaching 18 mu copper foils to the upper part and the lower part of the bonding sheets, and putting the bonding sheets into a vacuum hot press to press the bonding sheets to obtain the copper-clad plate. The pressing process is carried out under 1.5Mpa and 190 deg.C for at least 90 min.
The properties of the copper-clad laminate obtained are shown in Table 1.
Example two:
50g of hydantoin epoxy resin (MHR-154B, manufactured by Takebei tin-Etherchemical Co., Ltd.), 50g of phenyl silicone resin, 15g of siloxane oligomer containing hydroxyl (MP200, mechanical performance materials Inc.), 0.2g of hexynol, 0.10g of dispersant (BYK-110), 100g of rutile titanium dioxide and a proper amount of acetone solvent are added into a 500ml beaker, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 65 percent.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
Example three:
50g of hydantoin epoxy resin (MHR-154B, manufactured by Takebei tin-Etsu chemical Co., Ltd.), 50g of methyl phenyl silicone resin, 15g of siloxane oligomer containing hydroxyl (MP200, mechanical performance materials Inc.), 0.2 of hexynol, 0.10g of dispersant (BYK-110), 100g of rutile titanium dioxide and a proper amount of acetone solvent are added into a 500ml beaker, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 65 percent.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
Example four:
30g of hydantoin epoxy resin (MHR-154B, manufactured by Takebei tin-Etsu chemical Co., Ltd.), 70g of methylphenyl silicone resin, 10g of siloxane oligomer containing hydroxyl (MP200, mechanical performance materials Inc.), 0.4g of hexynol, 0.10g of dispersant (BYK-110), 100g of rutile titanium dioxide and a proper amount of acetone solvent are added into a 500ml beaker, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 65 percent.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
COMPARATIVE EXAMPLE one (in contrast to the example)
Weighing 100g of methyl vinyl silicone resin, dissolving the methyl vinyl silicone resin in 70g of methyl terminal vinyl silicone oil, adding 18.0g of methyl hydrogen-containing silicone oil and 0.10g of BYK-903 dispersant (manufactured by BYK company, Germany) after uniform dissolution, weighing 0.00005g of hexynol after uniform high-speed stirring, adding 0.005g of platinum-methyl vinyl complex after stirring for 30min, adding 100g of rutile titanium dioxide after continuous stirring for 30min, adding the mixture into a 500ml beaker, and uniformly stirring and mixing to obtain the organic silicon resin glue solution.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
The test method comprises the following steps:
1) prepreg (PP): after the smear was oven dried, if the PP sticky hand is recorded as ●, the non-sticky hand is recorded as O.
2) The method for testing the peeling Strength (Peel Strength, PS for short) comprises the following steps: the test was carried out using IPC-TM-6502.4.8 method.
3) Color difference value: the new physical quantity characterizing the luminous brightness of the LED and various light reflection characteristics of the substrate is the color difference value (delta E ab). The color difference value comprehensively represents the contribution of the substrate to the luminous efficiency of the LED. When the substrate is discolored and the light reflectivity is greatly reduced, the color difference value is large. The color difference value (Δ E ab) is influenced by three change values, namely the color difference change of the heating treatment (Δ a), the color difference change of the UV treatment (Δ b), and the change of the LED brightness after a certain operating time (Δ L). The color difference value (Δ Ε ab) can be expressed by the following formula: (Δ E × ab) ═ Δ a × 2+ Δ b × 2+ Δ L × 2)1/2. Test sample size: 50X 50(mm), 5 in number, substrates after etching, L, a and b values of the substrates were measured, the samples after the measurement were put into a hot air dryer at 200 ℃ for 20 hours for heat treatment, after cooling, L, a and b values thereof were measured, and values of changes before and after the substrate treatment (Δ L, Δ a and Δ b) were calculated using the formula (Δ E ab) ═ 2+ Δ b 2+ Δ L2)1/2The color difference value (n-5 average) was calculated.
4) Reflectance ratio: the double-sided copper-clad laminate was cut into a size of 50 × 50mm with a dicing saw, and then the surface copper foil was removed by etching to obtain a sample for measurement. The reflectance at 457nm (average value of n-5) of the measurement sample was measured using a spectrocolorimeter (manufactured by KONICA MINOLTA, inc.: CM3610d) in accordance with JIS Z-8722.
5) Reflectance after heating: the sample obtained in 1) was subjected to a heat treatment in a hot air dryer at 200 ℃ for 20 hours, and then the reflectance (average value of n: 5) was measured in the same manner as the measurement of the reflectance.
6) Reflectance after light irradiation: the sample obtained in 1) above was subjected to ultraviolet light (wavelength: 295-450 nm) illumination degree of 100mW/cm2After 24 hours of light irradiation treatment, the reflectance (average value of n 5) was measured in the same manner as the measurement of the reflectance.
7) Tg (glass transition temperature): a dynamic mechanical property tester (TA DMA Q800, USA) is adopted, and the thickness of the sample is 0.80 mm. The temperature test range is 50-350 ℃, the vibration frequency is 1Hz, the heating rate is 3 ℃/min, and the atmosphere is nitrogen;
8) CTE (X/Y ppm/DEG C): heating at 10 deg.C per minute from 30 deg.C to 350 deg.C by using thermal mechanical analyzer (TA INSTRUMENTS), measuring linear expansion coefficient in surface direction of 50 deg.C to 130 deg.C, wherein the measurement direction is longitudinal direction (Y) and transverse direction (X) of glass cloth surface;
9) water absorption rate*6: taking 3 samples of 10cm multiplied by 10cm, with the thickness of 0.80mm and with metal foils removed on two sides, drying at 100 ℃ for 2 hours, putting the samples into a dryer for cooling and weighing, then processing the samples for 5 hours at 121 ℃ and 2 atmospheric pressures by using a Pressure Cooker test machine, sucking free water on the surface of the water, putting the samples into the dryer for cooling and weighing, and calculating the water absorption of the plate according to the front weight and the rear weight.
10) Moist heat resistance (PCT): 3 samples of 10cm × 10cm, 0.80mm in thickness and having both sides free of metal foil were dried at 105 ℃ for 2 hours, treated at 121 ℃ under 2 atmospheres for 5 hours using a Pressure Cooker test (Pressure Cooker test), and then subjected to immersion tin in a tin furnace at 288 ℃ for 10 minutes to visually observe whether or not delamination occurred. If there are 0, 1, 2, 3 blocks in the 3 blocks, the layering phenomena are respectively recorded as 0/3, 1/3, 2/3, 3/3.
The properties of the copper-clad laminate obtained are shown in table 1:
TABLE 1
From table 1, it can be seen that:
the first comparative example has excellent yellowing resistance, low water absorption and thermal expansion coefficient and excellent wet heat resistance, but has too low peel strength of only 0.19N/mm, and is also difficult to be applied in the field of copper clad laminates.
In conclusion, the siloxane oligomer and/or alicyclic/hydrogenated acid anhydride and the polymerization inhibitor are added into the hydantoin epoxy resin and the silicone resin, so that the prepared resin composition, the prepreg and the laminated board have the characteristics of excellent yellowing resistance, heat resistance, humidity resistance, low water absorption rate, low thermal expansion coefficient and the like, and are very suitable for being applied to the field of copper-clad plates.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The resin composition is characterized by comprising the following components in parts by mass:
hydantoin epoxy resin: 5-85 parts by mass;
silicone resin: 15-95 parts by mass;
siloxane oligomer containing amino or hydroxyl groups: 1-55 parts by mass;
polymerization inhibitor hexynol: 0.01 to 10 parts by mass;
filling: 10-260 parts by mass;
coupling and/or dispersing agents: 0.01-5 parts by mass;
wherein the total of the hydantoin epoxy resin and the silicone resin is 100 parts by mass.
2. The resin composition of claim 1, wherein the hydantoin epoxy resin has the structure:
wherein R is1And R2Is a hydrogen atom or a methyl or ethyl group, R1And R2The same or different, and n is an integer of 1 to 6.
3. The resin composition according to claim 1, wherein the silicone resin is a condensation type silicone resin.
4. The resin composition according to claim 3, wherein the silicone resin is at least one of a methyl silicone resin, a phenyl silicone resin, and a methylphenyl silicone resin.
5. The resin composition according to claim 1, wherein the filler is any one of zinc oxide, aluminum oxide, titanium dioxide, silica, montmorillonite, calcium carbonate, or any combination thereof.
6. The resin composition according to claim 1, wherein the coupling agent is a silane coupling agent or a titanate coupling agent; the dispersing agent is a high molecular polymer with an acid value of 10-260 mg KOH/g.
7. A prepreg, characterized in that a solvent is added to the resin composition according to any one of claims 1 to 6 to dissolve the resin composition to form a glue solution, a reinforcing material is immersed in the glue solution, and the immersed reinforcing material is heated and dried to obtain the prepreg.
8. A laminate which is obtained by coating at least one prepreg according to claim 7 on one or both sides with a metal foil and hot-press forming.
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| CN201811395824.8A CN109504037B (en) | 2018-11-22 | 2018-11-22 | Resin composition, and prepreg and laminated board prepared from same |
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| CN201811395824.8A CN109504037B (en) | 2018-11-22 | 2018-11-22 | Resin composition, and prepreg and laminated board prepared from same |
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| Publication Number | Publication Date |
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| CN109504037A CN109504037A (en) | 2019-03-22 |
| CN109504037B true CN109504037B (en) | 2021-10-22 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104238A (en) * | 1976-11-23 | 1978-08-01 | Westinghouse Electric Corp. | Silica-alumina trihydrate filled epoxy castings resistant to arced SF6 |
| CN101218285A (en) * | 2005-05-12 | 2008-07-09 | 利昌工业株式会社 | White prepreg, white laminated plate, and metal foil clad white laminated plate |
| CN104893253A (en) * | 2015-07-02 | 2015-09-09 | 高旭 | LED (light-emitting diode) packaging material |
| CN106467668A (en) * | 2015-08-19 | 2017-03-01 | 广东生益科技股份有限公司 | A kind of organic siliconresin aluminum-based copper-clad plate and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633770B (en) * | 2009-08-28 | 2011-07-20 | 番禺南沙殷田化工有限公司 | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same |
-
2018
- 2018-11-22 CN CN201811395824.8A patent/CN109504037B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104238A (en) * | 1976-11-23 | 1978-08-01 | Westinghouse Electric Corp. | Silica-alumina trihydrate filled epoxy castings resistant to arced SF6 |
| CN101218285A (en) * | 2005-05-12 | 2008-07-09 | 利昌工业株式会社 | White prepreg, white laminated plate, and metal foil clad white laminated plate |
| CN104893253A (en) * | 2015-07-02 | 2015-09-09 | 高旭 | LED (light-emitting diode) packaging material |
| CN106467668A (en) * | 2015-08-19 | 2017-03-01 | 广东生益科技股份有限公司 | A kind of organic siliconresin aluminum-based copper-clad plate and preparation method thereof |
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| CN109504037A (en) | 2019-03-22 |
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