CN116082793B - Epoxy resin composition for yellowing-resistant white copper-clad plate, prepreg and substrate - Google Patents

Epoxy resin composition for yellowing-resistant white copper-clad plate, prepreg and substrate Download PDF

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CN116082793B
CN116082793B CN202211696673.6A CN202211696673A CN116082793B CN 116082793 B CN116082793 B CN 116082793B CN 202211696673 A CN202211696673 A CN 202211696673A CN 116082793 B CN116082793 B CN 116082793B
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epoxy resin
parts
titanium dioxide
yellowing
resin composition
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CN116082793A (en
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陈盛栋
涂发全
姚京松
孙益军
罗家宝
唐锋
黄飞霞
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DONGGUAN ITEQ CORP
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

The invention discloses an epoxy resin composition for a yellowing-resistant white copper-clad plate, which comprises the following raw materials in parts by weight: 15-40 parts of polyester resin, 10-20 parts of alicyclic epoxy resin, 20-35 parts of other epoxy resin, 20-40 parts of curing agent and 120-180 parts of inorganic filler. The resin composition adopts polyester resin and cycloaliphatic epoxy resin, so that the composition has excellent yellowing resistance, and the composition has higher initial whiteness due to high transparency of the polyester resin; in addition, the resin composition selects a high Tg curing agent to enable the curing agent to have high Tg and high heat resistance; and the resin composition selects rutile titanium dioxide subjected to surface treatment, so that the sedimentation of the titanium dioxide in the processing process of the resin solution is greatly improved, and the prepared copper-clad laminate has uniform higher initial whiteness and can be prepared into copper-clad laminates suitable for the backlight application requirements of circuit boards such as Mini LEDs of various electronic screens.

Description

Epoxy resin composition for yellowing-resistant white copper-clad plate, prepreg and substrate
Technical Field
The invention relates to the technical field of copper-clad laminates, in particular to an epoxy resin composition, a prepreg and a substrate for a yellowing-resistant white copper-clad plate.
Background
Mini LEDs are regarded as the leading technology of Micro light emitting diodes (Micro LEDs) of the next generation display technology, and are applied to devices such as pen phones, mobile phones, small-space displays, vehicle displays, televisions and the like by using the direct type backlight concept, so that the differential backlight high-order models are expected to be balanced with OLED high-order models. Meanwhile, mini LEDs have been used as a leading technology for Micro LEDs, and have also been used as a transition for Micro LEDs. With the increasing progress of technology, optical semiconductor LEDs and electronic devices are applied to more and more fields, and with the development of optical semiconductor technology and the continuous improvement of user needs, the power of optical semiconductor LEDs is continuously increased, the volume is gradually reduced, and the requirements on the stability and reliability of materials are higher and higher.
The white copper-clad plate material not only needs high initial state reflectivity, but also needs the characteristic of keeping the reflectivity for a long time. The latter is more difficult than the former in terms of the technical difficulty of achieving the two aspects, and the reflectivity of the general white copper-clad plate material is reduced due to two external condition factors: high heat radiation can cause obvious color change of the surface of a common substrate; the color change can be caused by long-time ultraviolet irradiation, so that the whiteness of the original plate surface is reduced. The white copper-clad plate material is more important to the increasingly severe use environment of the current stage, and the excellent yellowing resistance is added while the high initial state reflectivity of the material is emphasized. Although titanium dioxide provides higher initial state reflectivity in China patent CN 107629748A, the resin system can not provide excellent yellowing resistance and poor heat resistance because of adopting general epoxy resin and phenolic resin as main bodies and dicyandiamide as a curing agent, and can not meet the material requirement of the current Mini LED; in addition, in Chinese patent CN 101005948B, polyimide for Mitsubishi gas is used for preparing a white metal foil laminated plate, and the yellowing resistance of the plate can also meet the requirement, but the polyimide product has the problem of insufficient peeling strength when being bonded with a metal foil, and the problem of easy line peeling in the subsequent element mounting process is solved. And polyimide resin is difficult to achieve complete colorless transparency, so that the whiteness of the plate is still poor and the reflectivity of the plate to LED light is low when the ultra-white plate is prepared.
Therefore, developing a resin composition with high reflectivity, high glass transition temperature, high yellowing resistance, low CTE and other properties suitable for circuit board backlight applications of various electronic screen Mini LEDs and the like is an urgent need for development of the current industry.
Disclosure of Invention
In view of the above, the present invention aims at overcoming the drawbacks of the prior art, and its main purpose is to provide an epoxy resin composition, a prepreg and a substrate for a yellowing-resistant white copper-clad plate, and the copper-clad laminate manufactured by the epoxy resin composition has the properties of high reflectivity, high glass transition temperature, high yellowing resistance, low thermal expansion coefficient and the like, and is suitable for backlight application of circuit boards such as Mini LEDs of various electronic screens.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the epoxy resin composition for the yellowing-resistant white copper-clad plate comprises the following raw materials in parts by mass: 15-40 parts of polyester resin, 10-20 parts of alicyclic epoxy resin, 20-35 parts of other epoxy resin, 20-40 parts of curing agent and 120-180 parts of inorganic filler, wherein the total mass of the polyester resin, the alicyclic epoxy resin, the other epoxy resin and the curing agent is 100 parts.
As a preferable mode, the structural formula of the polyester resin is:
Wherein R 1 is-CH 2 or-C (CH 3)2,R2 is-CH 3 or-CH 2CH3 or-H, n=1, 2, 3), the polyester resin is polyester with benzene ring in the main chain synthesized by dihydric phenol and dibasic acid, the structural polyester resin has higher glass transition temperature than common polyester resin, and the terminal phenolic hydroxyl can improve the reactivity of an alicyclic epoxy system.
As a preferred embodiment, the cycloaliphatic epoxy resin comprises at least one of the following structural formulas:
The alicyclic epoxy resin has low reactivity, and when the alicyclic epoxy resin is excessively added, the system reaction is slow, and the production and the processing are not facilitated, so that the reactivity of the system is required to be improved by matching with the polyester resin with a specific proportion, and the mass ratio of the polyester resin to the alicyclic epoxy resin is 1 (0.25-0.75).
As a preferred embodiment, the other epoxy resin comprises at least one of the following structural formulas:
As a preferred scheme, the curing agent is a mixture of 4,4 '-diaminodiphenyl sulfone and styrene maleic anhydride, wherein the mass ratio of the 4,4' -diaminodiphenyl sulfone to the styrene maleic anhydride is 1 (4-6).
As a preferable scheme, the inorganic filler is a mixture of titanium dioxide and other inorganic fillers, the mass ratio of the titanium dioxide is more than 60%, the titanium dioxide is rutile titanium dioxide subjected to surface treatment, and the other inorganic fillers are one or more of aluminum hydroxide, boehmite, silicon dioxide and barium sulfate; the preparation method of the rutile titanium dioxide subjected to the surface treatment comprises the steps of mixing and stirring 200 parts of rutile titanium dioxide, 150 parts of butanone and 4 parts of surface treatment agent for 2 hours at 45 ℃, wherein the surface treatment agent is amino silane or epoxy silane.
As a preferable scheme, the flame retardant agent further comprises 5-15 parts of flame retardant, 0.01-1 part of antioxidant, 0.01-1 part of curing accelerator and 0.01-1 part of coupling agent; the flame retardant is one or more of triphenyl phosphate, resorcinol bis (diphenyl phosphate), 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxidation-10-phosphaphenanthrene-10-oxide, 2, 6-di (2, 6-dimethylphenyl) phosphinophenone, 10-phenyl-9, 10-dihydro-9-oxidation-10-phosphaphenanthrene-10-oxide or polyphenoxyphosphazene and derivatives thereof; the antioxidant is one or more of hindered phenol antioxidants, thiodipropionic acid diester antioxidants and phosphite antioxidants; the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.
As a preferable mode, the mass ratio of the polyester resin to the alicyclic epoxy resin is 1 (0.25-0.75).
The prepreg is prepared by dissolving the epoxy resin composition for the yellowing-resistant white copper-clad plate to prepare a glue solution, then dipping the reinforcing material in the glue solution, and then heating and drying the dipped reinforcing material.
A substrate made of the aforementioned prepreg.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and in particular, the technical scheme can be as follows:
The resin composition for the yellowing-resistant white copper-clad plate adopts polyester resin with good oxidation resistance and cycloaliphatic epoxy resin, so that the composition has excellent yellowing resistance, and has higher initial whiteness due to high transparency of the polyester resin; in addition, the resin composition for the yellowing-resistant white copper-clad plate selects the high Tg curing agent 4,4' -diaminodiphenyl sulfone and anhydride to be matched for use, so that the resin composition has high Tg and high heat resistance; and the resin composition for the yellowing-resistant white copper-clad plate selects rutile type titanium dioxide subjected to surface treatment, so that the sedimentation of the titanium dioxide in the processing process of a resin solution is greatly improved, and the prepared copper-clad laminate has uniform higher initial whiteness and can be prepared into copper-clad laminates suitable for the backlight application requirements of circuit boards such as Mini LEDs of various electronic screens.
In order to more clearly illustrate the features and effects of the present invention, the present invention will be described in detail with reference to specific examples.
Detailed Description
The invention discloses an epoxy resin composition for a yellowing-resistant white copper-clad plate, which comprises the following raw materials in parts by weight: 15-40 parts of polyester resin, 10-20 parts of alicyclic epoxy resin, 20-35 parts of other epoxy resin, 20-40 parts of curing agent and 120-180 parts of inorganic filler; wherein the polyester resin, the alicyclic epoxy resin, the other epoxy resin, and the curing agent total 100 parts by mass.
The structural formula of the polyester resin is as follows:
Wherein R 1 is-CH 2 or-C (CH 3)2,R2 is-CH 3 or-CH 2CH3 or-H, n=1, 2, 3), the polyester resin is polyester with benzene ring in the main chain synthesized by dihydric phenol and dibasic acid, the structural polyester resin has higher glass transition temperature than common polyester resin, and the terminal phenolic hydroxyl can improve the reactivity of an alicyclic epoxy system.
The cycloaliphatic epoxy resin comprises at least one of the following structural formulas:
The alicyclic epoxy resin has low reactivity, and when the alicyclic epoxy resin is excessively added, the system reaction is slow, and the production and the processing are not facilitated, so that the reactivity of the system is required to be improved by matching with the polyester resin with a specific proportion, and the mass ratio of the polyester resin to the alicyclic epoxy resin is 1 (0.25-0.75).
The other epoxy resin comprises at least one of the following structural formulas:
The curing agent is a mixture of 4,4 '-diaminodiphenyl sulfone and styrene maleic anhydride, wherein the mass ratio of the 4,4' -diaminodiphenyl sulfone to the styrene maleic anhydride is 1 (4-6).
The inorganic filler is a mixture of titanium dioxide and other inorganic fillers, the mass ratio of the titanium dioxide is more than 60%, the titanium dioxide is rutile titanium dioxide subjected to surface treatment, and the other inorganic fillers are one or more of aluminum hydroxide, boehmite, silicon dioxide and barium sulfate; the preparation method of the rutile titanium dioxide subjected to the surface treatment comprises the steps of mixing and stirring 200 parts of rutile titanium dioxide, 150 parts of butanone and 4 parts of surface treatment agent at 45 ℃ for 2 hours.
5-15 Parts of flame retardant, 0.01-1 part of antioxidant, 0.01-1 part of curing accelerator and 0.01-1 part of coupling agent; the flame retardant is one or more of triphenyl phosphate, resorcinol bis (diphenyl phosphate), 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxidation-10-phosphaphenanthrene-10-oxide, 2, 6-di (2, 6-dimethylphenyl) phosphinophenone, 10-phenyl-9, 10-dihydro-9-oxidation-10-phosphaphenanthrene-10-oxide or polyphenoxyphosphazene and derivatives thereof; the antioxidant is one or more of hindered phenol antioxidants, thiodipropionic acid diester antioxidants and phosphite antioxidants; the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.
The mass ratio of the polyester resin to the alicyclic epoxy resin is 1 (0.25-0.75).
The invention also discloses a prepreg, which is prepared by dissolving the epoxy resin composition for the yellowing-resistant white copper-clad plate to prepare a glue solution, then dipping the reinforcing material in the glue solution, and then heating and drying the dipped reinforcing material.
The invention also discloses a substrate which is prepared from the prepreg.
The following describes in detail specific embodiments.
The raw materials of the composition are represented by the following code numbers:
(A) Polyester resin
(B1) Cycloaliphatic epoxy resin:
(B2) Cycloaliphatic epoxy resin:
(B3) Cycloaliphatic epoxy resin:
(C1) Bisphenol A type phenolic epoxy resin
(C2) Hydrogenated bisphenol A type phenolic epoxy resin
(C3) Hydantoin epoxy resin (D1) 4,4' -diaminodiphenyl sulfone (D2) styrene-maleic anhydride EF-30
(D3) Phenolic resin
(E1) Surface treated rutile titanium dioxide
(E2) Boehmite of boehmite
(F) Poly (phenoxy) phosphazene
(G) Antioxidant 1010
(H) 2-ethyl-4-methylimidazole (I) silane coupling agent
The raw material ratios of the examples and the raw material ratios of the comparative examples are shown in tables 1 and 2, respectively.
Table 1:
Table 2:
adding the resin into a proper amount of solvent according to the proportion of the table 1 and the table 2, uniformly mixing, coating on a reinforcement material 2116 specification E-Glass, baking for 2-3min in an oven at 171 ℃ to obtain prepregs, respectively coating 1O oz copper foil on 6 prepregs as a lamination structure, putting into a laminating machine, laminating to obtain a laminated board, and carrying out performance test on the laminated board; the test method is as follows:
(1) Initial reflectance: the reflectance at 450nm was measured for the measurement sample by using a spectrocolorimeter in accordance with JIS Z-8722 to characterize the initial whiteness.
(2) After the sample obtained in the above (1) was subjected to heat treatment in an oven at 200℃for 1 hour, the reflectance was measured in the same manner as in the measurement of the reflectance, and the difference from the initial reflectance was indicative of the yellowing resistance.
(3) Peel strength: the test was specified according to IPC-TM-650.2.4.9.
(4) Glass transition temperature (Tg): the measurement was carried out according to the DSC method defined in IPC-TM-650.2.4.25 by Differential Scanning Calorimetry (DSC).
(5) Thermal stratification time (T-288): measured according to the IPC-TM-650.2.4.24.1 method.
(6) Water absorption rate: the samples with both sides copper foil removed were cooked in a pressure cooker at 121℃and 105kPa for 1 hour, and the water absorption was calculated from the weights before and after the cooking.
(7) Coefficient of Thermal Expansion (CTE): the determination was carried out according to the IPC-TM-650.2.4.24 method.
The test results of the above examples and comparative examples are shown in tables 3 and 4, respectively.
Table 3:
table 4:
Data analysis is carried out on table 3, so that the copper clad laminate obtained by the epoxy resin composition provided by the invention has high initial reflectivity, high reflectivity after heating, high glass transition temperature, low CTE and other performances, and can meet the requirements of circuit board backlight application of Mini LEDs and the like. Data analysis is carried out on the table 4, and compared with the examples 1-7, the comparative example 1 does not adopt polyester resin, and the initial reflectivity of the prepared copper-clad plate is low; compared with the examples 1-7, the comparative example 2 adopts phenolic resin as a curing agent, and the prepared copper-clad plate has low initial reflectivity, larger change of reflectivity after being heated and poorer yellowing resistance; compared with the comparative examples 1-7, the comparative example 3 is added with excessive polyester resin, and the prepared copper-clad plate has high initial reflectivity and excellent yellowing resistance, but has lower Tg and cannot be applied to Mini LED circuit boards; compared with the comparative examples 1-7, the prepared copper-clad plate has high initial reflectivity but poor yellowing resistance and cannot be applied to Mini LED circuit boards without adopting alicyclic epoxy resin; compared with the comparative examples 1-7, the comparative example 5 adopts hydantoin epoxy resin with excellent yellowing resistance, but does not adopt alicyclic epoxy resin, and the prepared copper-clad plate has high initial reflectivity and good yellowing resistance, but has higher water absorption, water is easy to remain in the product to influence the performance, and can not be applied to Mini LED circuit boards; compared with examples 1-7, the inorganic filler used in comparative example 6 has less than 60% of titanium dioxide, and the prepared copper-clad plate has lower initial reflectivity and cannot be applied to Mini LED circuit boards.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical principles of the present invention are still within the scope of the technical solutions of the present invention.

Claims (5)

1. An epoxy resin composition for a yellowing-resistant white copper-clad plate is characterized in that: the raw materials comprise the following components in parts by weight: 15-40 parts of polyester resin, 10-20 parts of alicyclic epoxy resin, 20-35 parts of other epoxy resin, 20-40 parts of curing agent and 120-180 parts of inorganic filler, wherein the total mass of the polyester resin, the alicyclic epoxy resin, the other epoxy resin and the curing agent is 100 parts;
wherein the curing agent is a mixture of 4,4 '-diaminodiphenyl sulfone and styrene maleic anhydride, and the mass ratio of the 4,4' -diaminodiphenyl sulfone to the styrene maleic anhydride is 1 (4-6);
The inorganic filler is a mixture of titanium dioxide and other inorganic fillers, the mass ratio of the titanium dioxide in the inorganic filler is more than 60%, the titanium dioxide is rutile titanium dioxide subjected to surface treatment, and the other inorganic fillers are one or more of aluminum hydroxide, boehmite, silicon dioxide and barium sulfate; the preparation method of the rutile titanium dioxide subjected to the surface treatment comprises the steps of mixing 200 parts by mass of rutile titanium dioxide, 150 parts by mass of butanone and 4 parts by mass of surface treatment agent at 45 ℃ and stirring for 2 hours to obtain the rutile titanium dioxide;
The structural formula of the polyester resin is as follows:
Wherein R 1 is-CH 2 or-C (CH 3)2,R2 is-CH 3 or-CH 2CH3 or-H, n=1, 2,3;
The cycloaliphatic epoxy resin comprises at least one of the following structural formulas:
the mass ratio of the polyester resin to the alicyclic epoxy resin is 1 (0.25-0.75).
2. The epoxy resin composition for yellowing-resistant white copper-clad laminate according to claim 1, wherein: the other epoxy resin comprises at least one of the following structural formulas:
Wherein/> And
N=1, 2,3 in the formula.
3. The epoxy resin composition for yellowing-resistant white copper-clad laminate according to claim 1, wherein: further comprises 5-15 parts of flame retardant, 0.01-1 part of antioxidant, 0.01-1 part of curing accelerator and 0.01-1 part of coupling agent; the flame retardant is one or more of triphenyl phosphate, resorcinol bis (diphenyl phosphate), 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxo-10-phosphafei-10-oxide, 2, 6-di (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxo-10-phosphafei-10-oxide or polyphenoxyphosphazene; the antioxidant is one or more of hindered phenol antioxidants, thiodipropionic acid diester antioxidants and phosphite antioxidants; the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.
4. A prepreg, characterized in that: dissolving the epoxy resin composition for the yellowing-resistant white copper-clad plate according to any one of claims 1 to 3 to prepare a glue solution, then dipping a reinforcing material in the glue solution, and then heating and drying the dipped reinforcing material to prepare the prepreg.
5. A substrate, characterized in that: which is produced from the prepreg according to claim 4.
CN202211696673.6A 2022-12-28 2022-12-28 Epoxy resin composition for yellowing-resistant white copper-clad plate, prepreg and substrate Active CN116082793B (en)

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