TW201932303A - Laminated substrate and printed circuit board thereof - Google Patents

Abstract

The present invention provides alaminated substrate and printed circuit board. The laminated substrate includes an epoxy resin composition, the epoxy resin composition includes 100 parts by weight of an organic solid, 30 to 70 parts by weight of an inorganic filler, 0.01 to 1 parts by weight of a curing accelerator, and 0.01 to 1 part by weight of a silane coupling agent; Wherein the organic solid includes: 60 to 80 parts by weight of an epoxy resin and 20 to 40 parts by weight of a curing agent. The epoxy resin composition of the present invention is suitable for laminated substrate, as well as effectively increases the glass transition temperature and provides better heat resistance and machinability of the laminated substrate and printed circuit board.

Description

Laminates and printed circuit boards

The present invention relates to a laminate and a printed circuit board, and more particularly to a laminate and a printed circuit board using an epoxy resin composition.

Printed circuit boards (PCBs) are widely used in everyday electrical products, and with the development of electronic products, PCB lines tend to be highly dense. Therefore, the demand for safety and reliability of electrical products is relatively high. In particular, when a printed circuit board is used in a high-temperature, humid or polluted environment, the surface of the printed circuit board tends to accumulate dust, water, or contaminants, thereby generating partial discharge, forming a conductive or partially conductive passage, and the surface of the insulating layer. It is prone to leakage and sparks, which reduces the insulation. In severe cases, it will break through the short circuit/open circuit and even cause a fire phenomenon, which will bring a big safety hazard. In order to improve the insulation, safety and reliability of electrical products under high temperature, humidity and easy pollution conditions, the tracking resistance index (CTI) of printed circuit board materials has been paid more and more attention.

On the other hand, under the trend of lead-free, the existing component soldering processing method is replaced by the lead-free soldering processing method, resulting in a soldering temperature higher than 20 ° C compared with the lead-containing soldering process, and further, outdoor charging equipment, voltage converter Such as the rapid development of circuit boards, therefore, the high heat resistance and reliability of the CTI copper-clad board material are higher than the requirements. For the existing high CTI FR-4 sheet, an amine-based resin is used, which has low heat resistance, low glass transition temperature (Tg) and insufficient chemical resistance, and is difficult to meet the requirements of multi-layer processing and lead-free soldering.

In the prior art, CN 101654004 B uses a low bromine epoxy resin as a main component, and dicyandiamide (DICY) as a curing agent, although providing a better comparison of the leakage tracking index The number, but its heat resistance is poor, it is difficult to meet the needs of lead-free processing methods. In addition, CN 105419231 A uses alicyclic epoxy resins, phosphorus-containing epoxy resins, brominated epoxy resins, acid anhydrides, and phosphorus-containing phenolic aldehydes to provide better tracking index and heat resistance compared to leakage, but its glass transition The lower temperature limits the PCB processing process and still does not meet the current processing and use requirements of electronic materials.

In order to solve the above technical problem, one of the technical solutions adopted by the present invention is to provide a laminate comprising: a resin substrate comprising a plurality of prepreg films, and each of the prepreg films is made of a glass fiber The substrate is made by coating an epoxy resin composition; and a metal foil layer is disposed on at least one surface of the resin substrate; wherein the epoxy resin composition comprises: 100 parts by weight An organic solid, 30 to 70 parts by weight of an inorganic filler, 0.01 to 1 part by weight of a curing accelerator, and 0.01 to 1 part by weight of a monodecane coupling agent; wherein the organic solid comprises: 60 to 80% by weight And an epoxy resin; and 20 to 40 parts by weight of a curing agent; wherein the epoxy resin comprises a compound of the formula (I): , n is between 1 and 10.

In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a printed circuit board comprising the laminate of the present invention.

One of the advantageous effects of the present invention is that the laminate and the printed circuit board provided by the present invention can be promoted by "100 parts by weight of the organic solid, 30 to 70 parts by weight of the inorganic filler, and 0.01 to 1 part by weight of the curing agent. And 0.01 to 1 part by weight of a decane coupling agent" and "the epoxy resin comprises a compound of formula (I): , n is a 1 to 10" technical solution to meet the V0 flame retardant requirements of the plastic flammability standard UL-94 issued by Underwriters Laboratories, and has a very high contrast tracking index (CTI). .

L‧‧‧ Laminate

1‧‧‧Resin substrate

11‧‧‧Semi-cured film

111‧‧‧glass fiber substrate

112‧‧‧Epoxy resin composition

2‧‧‧metal foil layer

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a laminate provided in accordance with an embodiment of the present invention.

The embodiments of the present invention relating to "laminates and printed circuit boards" are described below by way of specific embodiments, and those skilled in the art can understand the advantages and effects of the present invention from the disclosure of the present specification. The invention can be implemented or applied in various other specific embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention.

It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements or signals, these elements or signals are not limited by these terms. These terms are primarily used to distinguish one element from another, or one signal and another. In addition, the term "or" as used herein may include a combination of any one or more of the associated listed items, depending on the actual situation.

In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide an epoxy resin composition laminate. Referring to FIG. 1 , a laminate L provided by the present invention includes: (a) a resin substrate 1, comprising a plurality of prepreg films 11, and each of said prepreg films 11 is made of a glass fiber substrate 121 coated with an epoxy resin composition 122 of the present invention; and (b) a metal foil layer 2. It is disposed on at least one surface of the resin substrate 1, or the metal substrate layer 2 is disposed above and below the resin substrate 1 as needed. The laminate L of the present invention is suitable for use in white goods, inverters, outdoor charging piles, and the like.

In more detail, the epoxy resin composition 122 includes: 100 parts by weight of an organic solid, 30 to 70 parts by weight of an inorganic filler, 0.01 to 1 part by weight of a curing accelerator, and 0.01 to 1 part by weight of a decane coupling. Wherein the organic solid comprises: 60 to 80 parts by weight of an epoxy resin; and 20 to 40 parts by weight of a curing agent; wherein the epoxy resin comprises a compound of the formula (I): , n is between 1 and 10.

Specifically, the epoxy resin further includes a group selected from the group consisting of the following compounds: as well as , where n is between 1 and 10.

Generally, in the epoxy resin composition, the curing agent chemically reacts with the epoxy resin to form a network-shaped three-dimensional polymer, and the linear resin becomes an additive of a tough solid type. Further, the curing agent of the present invention comprises an active ester compound, an aromatic diamine, an organic acid anhydride, a bisphenol, a dicyandiamide, and a linear phenolic resin curing agent. At least one of them. Specifically, the curing agent of the present invention includes diaminodiphenyl hydrazine (DDS), styrene-maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromobisphenol A (TBBA), bisphenol A (BPA). At least one of bisphenol S (BPS), dicyandiamide, phenol novolac resin, and cresol novolac resin.

The active ester compound of the present invention is selected from the following compounds: Wherein m, k and q are independently selected from 0 or 1, n is from 0.25 to 2, and R is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene Structure.

For example, such as:

Specifically, the active ester compound can be obtained by reacting a carboxylic acid compound with a hydroxy compound and/or a thiol compound.

Preferably, the active ester compound can be obtained by reacting a carboxylic acid compound with a phenol compound, and particularly preferably an aromatic compound obtained by reacting an active ester compound with a carboxylic acid compound and a naphthol compound, which is An aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule. The active ester compound can be linear or multi-branched. If the active ester compound has a compound having at least two carboxylic acids in its molecule and the compound having at least two carboxylic acids in the molecule contains an aliphatic chain, it can improve its compatibility with the epoxy resin, and when When it has an aromatic ring, heat resistance can be improved.

The carboxylic acid compound may, for example, be benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromelli-4. acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic acid, and isophthalic acid are preferred from the viewpoint of heat resistance; More preferably, isophthalic acid and terephthalic acid.

Specific examples of the hydroxy compound may be hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S , phenol, o-cresol m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-di Hydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglycine, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among them, in view of improving the heat resistance of the active ester compound, preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, and three. Hydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolac; more preferably, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxydiphenyl Ketone, dicyclopentadienyl diphenol and phenol novolac; particularly preferred are dicyclopentadienyl diphenol and phenol novolac. Since the dicyclopentadiene structure is a rigid structure, the effect of heat resistance is improved, and the effect of suppressing the coefficient of linear expansion is also obtained, and the substrate after molding can be prevented from being warped.

The active ester compound of the present invention may further comprise an amine structure for increasing the compatibility of the active ester compound with an epoxy resin and other hardeners, and the amine structure may be obtained by reactive crosslinking of the amine group-containing monomer. preferably diamine monomer, for example p-phenylenediamine (p-phenylene diamine), 4,4 '- oxydianiline (4,4' -oxydianiline), 3,4 ' - oxydianiline (3,4 ' -Oxydianiline), 2,2-bis(4-[4-aminophenoxy]phenyl)propane, 2,2-Bis(4-[4-aminophenoxy]phenyl)propane) 2-Bis(4-[3-aminophenoxy]phenyl)sulfone), 1,3-bis(4-aminophenoxy) A monomer such as 1,3-Bis(4-aminophenoxy)benzene is particularly preferred as 4,4'-oxydianiline-4,4'-diphenylamine.

For example, the active ester compound may be a resin having one or more ester groups in one molecule, or may be obtained by a synthetic modification of a commercially available product. For example, by DIC Synthetic and modified products such as "EXB-9460", "EXB-9470", "EXB-9480" and "EXB-9420" manufactured by the company. The method for producing the active ester compound is not particularly limited, and it can be produced by a known method. For example, it can be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound.

The active ester compound can react with the epoxy resin to form a network cross-linking structure containing no secondary hydroxyl group, and a network structure of a secondary alcoholic hydroxyl group is generated in a ring-opening reaction with respect to a general epoxy resin system. Lower dielectric properties and low water absorption properties. The active ester compound of the present invention comprises at least one ester group having high reactivity, preferably two or more ester groups, and the ester group may participate in the hardening reaction of the epoxy resin, and may form a network structure free of secondary alcohol hydroxyl groups. And it is difficult to form a polar group, thereby providing an excellent low dielectric constant, a low dielectric loss factor, high heat resistance, and low water absorption. Further, it is known from Japanese patents such as JP2002-012650, JP2003-082063, and JP2003-252958, when an active ester compound having a benzene ring, a naphthalene ring or a biphenyl structure is used as a hardener for an epoxy resin, compared with Conventional phenolic has lower dielectric constant and dielectric loss values.

On the other hand, inorganic fillers can be selected as needed, and the properties of the products can be improved by selecting different inorganic fillers, such as improving the heat dissipation conditions when the resin is cured, reducing the amount of epoxy resin to reduce the cost, increasing the toughness and impact resistance. Properties, mechanical strength, electrical conductivity, improve wear resistance and increase insulation properties. In the epoxy resin composition of the present invention, the inorganic filler is selected from the group consisting of cerium, cerium oxide, cerium aluminate, aluminum hydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, and oxidation. A group of aluminum, boehmite, clay, kaolin, talc, and mica. Preferably, it may be selected from the group consisting of aluminum hydroxide, boehmite, ceria, talc, and yttrium aluminate.

The curing accelerator is used for lowering the curing temperature of the epoxy resin and shortening the curing time. The curing accelerator preferred in the present invention is an imidazole curing accelerator. For example, the curing accelerator is selected from the group consisting of 2-methylimidazole and 2- A group consisting of ethyl-4-methylimidazole, 2-phenylimidazole, and 2-undecylimidazole.

Further, the epoxy resin composition of the present invention further includes an appropriate amount of a solvent, For example, ketones, esters, ethers, alcohols, etc., more specifically, the solvent of the present invention is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether, propylene glycol methyl ether acetate, and cyclohexanone. Group.

In addition, in the epoxy resin composition of the present invention, the decane coupling agent has the effects of improving mechanical properties and strengthening adhesion, and the decane coupling agent contains a long bond to form a flexible interface for stress relaxation. The layer absorbs and disperses the impact energy to obtain good impact strength and toughness. The inorganic functional group of the decane coupling agent is a trifunctional group, that is, Si ^- (OR ₂ ) ₃ . For example, the decane coupling agent may be vinyl decane, amino decane, methacryloxy decane or the like.

The present invention further provides an additional technical solution which is a printed circuit board comprising the laminate of the present invention. The printed circuit board provided by the invention can meet the design, development and application of various electronic products by the high glass transition temperature, high heat resistance and good mechanical processing performance of the laminate.

A plurality of sets of examples and comparative examples will be made below for the epoxy resin composition of the present invention to demonstrate optimum laminate characteristics by the specific composition ratio formulation of the present invention.

[First Embodiment]

First, the following resin compositions were uniformly mixed in a stirred tank according to the following Table 1 and placed in a dipping tank, and then the resin composition was applied to a reinforcing glass fiber cloth (E-Glass). The resin composition was attached to a glass fiber cloth, baked by heating, and baked in a 171 ° C oven for 3 to 5 minutes to form a semi-cured film to obtain a semi-cured film.

The semi-cured film obtained in batches above is taken from the same batch of semi-cured film four sheets and two 18 μm copper foils, laminated in the order of copper foil, four-ply semi-cured film and copper foil, and then under vacuum conditions. A copper foil substrate was formed by press-bonding at 220 ° C for 2 hours.

A1: Low bromine epoxy resin of formula (I) of the present invention

A2: BPA type phenolic epoxy resin

A3: Chain extended BPA epoxy resin

A4: Biphenyl type epoxy resin

B1: dicyandiamide (DICY)

B2: tetrabromobisphenol A (TBBA)

B3: Diaminodiphenyl hydrazine (DDS)

B4: styrene-maleic anhydride (EF-30)

B5: Novolac resin

B6: Bisphenol S (BPS)

B7: Active ester compound

C1: aluminum hydroxide

C2: Boehmite

C3: yttrium aluminate

D: diethyltetramethylimidazole

E: decane coupling agent

F: butanone

[First test case]

The test examples of the present invention further tested the properties of the laminates prepared in the above examples and comparative examples, the test methods are as follows, and the test results are recorded in Table 2:

(1) Water absorption rate: Since the copper-clad substrate is affected by the temperature and humidity of the environment, it will expand and deform or adsorb moisture, and in the case where the water content of the copper-clad substrate and the humidity are too high, the problem of explosion is likely to occur or other Defects of the board, etc., so the water absorption rate must be measured to determine the water absorption characteristics of the copper clad substrate. Conventionally, IR spectral analysis or thermal weight loss analysis can be performed on the material to confirm the water absorption of the copper-clad substrate.

(2) Heat resistance: Also known as "bleaching tin result", the heat resistance test is based on the industry standard IPC-TM-650 Method 2.4.13.1, soaking the copper-clad substrate in the 288 °C tin furnace to the time required for the explosion.

(3) Thermal stratification time T288: Measured according to the method of IPC-TM-650 2.4.24.1.

(4) Glass transition temperature (Tg): Measured according to the DSC method specified in IPC-TM-6502.4.25 according to differential scanning calorimetry (DSC).

(5) Flame-retardant characteristics: According to the UL94 vertical burning method, the flame-retardant grade of the plastic material is determined by the self-ignition time, the spontaneous combustion speed and the falling particle state of the plastic material standard test piece after flame combustion. According to the quality of the fire resistance, the order is HB, V-2, V-1, V-0, and the highest is 5V. The UL 94 test method refers to the plastic material to hang Burn in a straight way on the flame. The test cycle is performed every ten seconds. The steps are as follows: Step 1: Put the test piece into the flame for ten seconds and then remove it, and measure the test piece to continue burning time (T1) after the removal; Step 2: When the test piece flame After extinction, put it into the flame for ten seconds and then remove it, and then measure the sample to continue burning time (T2) after removal; Step 3: Repeat several experiments and take the average value; Step 4: Calculate T1+T2 total. The requirement of UL 94 V-0 is that the average of the single burning time T1 and the average T2 of the test piece shall not exceed 10 seconds, and the total of T1 and T2 shall not exceed 50 seconds to meet the requirements of UL 94 V-0. .

The high CTI epoxy resin composition laminate of the present invention and the printed circuit board have a tracking index (CTI) up to more than 600 V, and the copper clad laminate produced using the composition has a high glass transition temperature and a high Heat resistance and good machinability, flame retardant properties are more in line with UL94 standard V0 and other characteristics, can be applied to lead-free soldering.

[Advantageous Effects of Embodiments]

One of the advantageous effects of the present invention is that the laminate and the printed circuit board provided by the present invention can be promoted by "100 parts by weight of the organic solid, 30 to 70 parts by weight of the inorganic filler, and 0.01 to 1 part by weight of the curing agent. Agent, and 0.01 to 1 weight , n is a 1 to 10" technical solution to meet the V0 flame retardant requirements of the plastic flammability standard UL-94 issued by Underwriters Laboratories, and has a very high contrast tracking index (CTI). .

Furthermore, the laminates and printed circuit boards of the present invention have higher glass transition temperatures, high heat resistance and good machinability, and are suitable for lead-free soldering. A laminate suitable for use in a white goods, an inverter, an outdoor charging pile, or the like can be produced by using the resin composition of the present invention.

The above disclosure is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Therefore, any equivalent technical changes made by using the present specification and the contents of the drawings are included in the application of the present invention. Within the scope of the patent.

Claims (10)

A laminate comprising: a resin substrate comprising a plurality of prepreg films, each of the prepreg films being made of a glass fiber substrate coated with an epoxy resin composition; and a metal foil layer Provided on at least one surface of the resin substrate; wherein the epoxy resin composition comprises: (a) 100 parts by weight of an organic solid comprising: 60 to 80 parts by weight of an epoxy resin And 20 to 40 parts by weight of a curing agent; (b) 30 to 70 parts by weight of an inorganic filler; (c) 0.01 to 1 part by weight of a curing accelerator; and (d) 0.01 to 1 part by weight of one a decane coupling agent; wherein the epoxy resin comprises a compound of formula (I): , n is between 1 and 10. The laminate according to claim 1, wherein the epoxy resin composition further comprises: a solvent, and the solvent is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether, propylene glycol methyl ether acetate, and cyclohexanone. Group. The laminate according to claim 1, wherein the epoxy resin further comprises a compound selected from the group consisting of: as well as a group consisting of; wherein n is between 1 and 10. The laminate according to claim 1, wherein the curing agent is selected from the group consisting of an active ester compound, an aromatic diamine, an organic acid anhydride, a bisphenol, a dicyandiamide, and a novolac resin curing agent. Group. The laminate of claim 4, wherein the active ester compound is selected from the group consisting of: Wherein m, k and q are independently selected from 0 or 1, n is 0.25 to 2, and R is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene. structure. The laminate according to claim 1, wherein the curing agent is selected from the group consisting of diaminodiphenyl hydrazine, styrene-maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, diaminodiphenyl fluorene, tetrabromo A group consisting of bisphenol A, bisphenol A, bisphenol S, dicyandiamide, phenol novolac resin, and cresol novolac resin. The laminate according to claim 1, wherein the inorganic filler is selected from the group consisting of ruthenium and ruthenium Groups of cerium oxide, yttrium aluminate, aluminum hydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, boehmite, clay, kaolin, talc, and mica . The laminate according to claim 1, wherein the curing accelerator is an imidazole curing accelerator. The laminate according to claim 8, wherein the curing accelerator is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-undecylimidazole. The group formed. A printed circuit board comprising the laminate of claim 1.