CN110655757A - Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof - Google Patents

Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof Download PDF

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CN110655757A
CN110655757A CN201910926060.9A CN201910926060A CN110655757A CN 110655757 A CN110655757 A CN 110655757A CN 201910926060 A CN201910926060 A CN 201910926060A CN 110655757 A CN110655757 A CN 110655757A
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epoxy resin
prepreg
halogen
resin composition
curing agent
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CN110655757B (en
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邓瑞景
许红卫
窦伟
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Qingdao Ou Puri New Material Co Ltd
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Qingdao Ou Puri New Material Co Ltd
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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    • 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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    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/306—Resistant to heat
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Abstract

The invention provides a halogen-free resin composition, which comprises the following components: the weight portions are as follows: 400 portions of epoxy resin, 40-70 portions of curing agent A, 10-30 portions of curing agent B, 200 portions of inorganic filler, 0.1-0.8 portion of curing accelerator, 0.7-1.5 portions of coupling agent and 210 portions of solvent, wherein, the content of the components except the solvent is 60-75 percent. The prepreg prepared by adopting the halogen-free resin composition has a flat and smooth surface appearance and a very wide processing operation window. The laminated board prepared by using the curing sheet has the advantages of less surface appearance defects, high dimensional stability and excellent electrical insulation performance, and can meet the requirements of high-performance printed circuit board base materials.

Description

Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof
Technical Field
The invention relates to the technical field of electronic materials, in particular to a halogen-free epoxy resin composition, and a prepreg and a laminated board prepared from the halogen-free epoxy resin composition.
Background
In recent years, with the rapid development of computers, communication equipment and communication technologies, the integration level of electronic components is higher and higher, and electronic products are developed towards being light, thin, short and small, so that higher requirements are put forward on the fineness of printed circuit board processing and the circuit accuracy.
The traditional laminated board for the printed circuit mainly adopts brominated epoxy resin, tetrabromobisphenol A and other bromine-containing flame retardants to realize the flame retardant property of the board. However, the bromine-containing flame retardant generates harmful substances such as hydrogen bromide, dioxin, dibenzofuran and the like during combustion, seriously pollutes the environment and harms human health. Therefore, research on halogen-free flame retardant laminates has become a hot spot in the electronics industry.
As a substitute for the bromine-containing flame retardant, a resin mainly containing flame retardant elements such as nitrogen, phosphorus, silicon and the like, and an inorganic filler containing crystal water (such as aluminum hydroxide, magnesium hydroxide and the like) are introduced to improve the flame retardancy of the board, but the surface appearance of the prepreg and the wettability of the resin in the glass fiber cloth are affected.
Moreover, the conventional formula of the halogen-free flame-retardant copper-clad plate is usually cured by matching epoxy resin containing a DOPO structure with phenolic resin containing the DOPO structure, the two substances containing the DOPO structure have higher molecular weight and molecular structure steric hindrance and poorer wettability, and the cured surface has rough and uneven appearance. The prepreg prepared by the conventional halogen-free resin formula is used for preparing the copper-clad plate, the processing operation window is narrow, the appearance defects of the copper-clad plate surface are more, the dimensional stability is poor, the short circuit and open circuit defects are easy to occur in the subsequent circuit board processing process, and the high standard and high requirement of the high-performance printed circuit board on the processing fineness and the circuit accuracy can not be met.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
Aiming at one or more problems in the prior art, the invention aims to provide a halogen-free resin composition, and a prepreg and a laminated board prepared by using the halogen-free resin composition. The halogen-free resin composition can realize halogen-free flame retardance, and the flame retardance can reach UL 94V-0 level; the composition has excellent wettability in glass fiber cloth, so that the surface of a prepreg prepared from the composition is flat and smooth in appearance, and the processing operation window is extremely wide. The laminated board prepared by using the epoxy resin composition has the advantages of less surface appearance defects, high dimensional stability and excellent electrical insulation performance, and can meet the requirements of high-performance printed circuit board base materials.
The invention adopts the following technical scheme:
the invention provides a halogen-free resin composition, which comprises the following components:
the weight portions are as follows:
300 portions and 400 portions of epoxy resin,
40-70 parts of a curing agent A,
10-30 parts of a curing agent B,
130 portions and 200 portions of inorganic filler,
0.1 to 0.8 portion of curing accelerator,
0.7 to 1.5 portions of coupling agent,
150 portions of solvent and 210 portions of solvent,
wherein, the content of the components except the solvent is 60 to 75 percent.
Preferably, the following components are included:
the weight portions are as follows:
354 parts of epoxy resin, namely 354 parts of epoxy resin,
41 parts of a curing agent A, namely,
29 parts of a curing agent B, namely,
182 parts of an inorganic filler, namely an inorganic filler,
0.45 part of a curing accelerator,
1.5 parts of a coupling agent,
224 parts of a solvent, namely 224 parts of,
wherein, the content of the components except the solvent is 60 to 75 percent.
According to an aspect of the present invention, the epoxy resin includes one or a combination of two or more of a bisphenol a type epoxy resin, a phenol novolac type epoxy resin, a bisphenol a novolac type epoxy resin, an o-methyl novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, an isocyanate type epoxy resin, a tetrafunctional epoxy resin, or a phosphorous novolac epoxy resin.
Preferably, the phosphorus-containing novolac epoxy resin comprises one or more of DOPO modified novolac epoxy resin, DOPO-HQ modified novolac epoxy resin or DOPO-NQ modified novolac epoxy resin.
DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; DOPO-HQ is 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; DOPO-NQ is 10- (2, 5-dihydroxynaphthyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The structural formulas of the DOPO and the DOPO derivatives are as follows:
DOPO structural formula:
Figure BDA0002218954600000031
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
DOPO-HQ structural formula:
Figure BDA0002218954600000032
10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
DOPO-NQ structural formula:
Figure BDA0002218954600000041
10- (2, 5-dihydroxynaphthyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
According to one aspect of the present invention, the curing agent a includes one or a combination of two or more of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, p-xylidine, dicyandiamide, phenol novolac resin, bisphenol a type phenol resin, or phosphorus-containing phenol resin.
Preferably, the phosphorus-containing phenolic resin comprises one or more of DOPO modified phenolic resin, DOPO-HQ modified phenolic resin or DOPO-NQ modified phenolic resin.
DOPO is a flame retardant intermediate, DOPO and derivatives thereof can be used as reactive and additive flame retardants, DOPO and derivatives thereof can be used for synthesizing epoxy resin containing a DOPO structure and phenolic resin containing the DOPO structure, and the DOPO and derivatives thereof are mainly used in the conventional halogen-free flame-retardant copper-clad plate formula at present, the two substances containing the DOPO structure have larger molecular weight and molecular structure steric hindrance, poorer wettability, and rough and uneven surface appearance after curing.
The reaction formula of DOPO and DOPO-NQ and the epoxy resin is as follows:
Figure BDA0002218954600000042
reaction formula of DOPO and epoxy resin
Figure BDA0002218954600000051
Reaction formula of DOPO-NQ and epoxy resin
According to one aspect of the invention, the curing agent B is an organic phosphorus curing agent, and the structural formula of the curing agent B is as follows:
wherein R1 is an aliphatic group and R2 is an aliphatic group. The aliphatic space structure is relatively small, the wettability of the halogen-free resin composition can be better by reacting with the epoxy resin, and the reaction formula of the curing agent B and the epoxy resin is shown as follows. The better the wettability, the more the resin components in the grains of the glass fiber cloth, the more excellent the electrical insulation performance, and the less the defects of open circuit, short circuit and the like in the later PCB processing process such as drilling, copper deposition, electroplating and the like.
Reaction formula of curing agent B and epoxy resin
According to one aspect of the invention, the inorganic filler comprises one or a combination of two or more of silica, magnesium hydroxide, mica powder, kaolin, talc, calcium carbonate or aluminum hydroxide.
Preferably, the inorganic filler is an inorganic filler surface-treated with a silane coupling agent.
According to an aspect of the present invention, the halogen-free resin composition further comprises a flame retardant in an amount of 20 parts by weight or less, preferably 10 parts by weight or less.
In the formula of the halogen-free resin composition, phosphorus is mainly used for flame retardance, and if the phosphorus-containing epoxy resin or the phosphorus-containing curing agent in the formula contains more phosphorus, the phosphorus content reaches a certain amount, the flame retardance grade can meet the requirement, and a flame retardant is not needed. If the phosphorus-containing epoxy resin and the phosphorus-containing curing agent are less in component and the phosphorus content is insufficient, the flame retardant needs to be supplemented to meet the requirement of flame retardant grade.
According to one aspect of the invention, the flame retardant comprises one or a combination of two or more of triphenyl phosphate, ammonium polyphosphate, condensed phosphate, phosphazene, aluminum hypophosphite, aluminum diethylphosphinate, melamine polyphosphate or melamine cyanurate. The flame retardant is added additionally according to the requirement of the flame retardant property of the material.
According to one aspect of the invention, the cure accelerator comprises an imidazole accelerator and/or an organometallic salt.
Preferably, the imidazole-based accelerator comprises 2-ethyl-4-methylimidazole or 2-methylimidazole.
Preferably, the organometallic salt comprises aluminum acetylacetonate or cobalt acetylacetonate.
According to one aspect of the invention, the coupling agent is a silane coupling agent.
According to one aspect of the invention, the solvent comprises one or a combination of two or more of acetone, butanone, dimethylformamide, propylene glycol methyl ether acetate or cyclohexanone.
The invention also provides a preparation method of the halogen-free resin composition, which adopts the components of the halogen-free resin composition and comprises the following steps:
mixing solid components in epoxy resin and curing agent in the halogen-free resin composition with partial solvent, and stirring to completely dissolve the solid components in the solvent;
adding the liquid components, and stirring until the liquid components are uniformly mixed; and
then adding the solid flame retardant, the inorganic filler and the residual solvent, and stirring until the mixture is uniformly mixed to obtain the halogen-free resin composition.
In the halogen-free resin composition, some of the epoxy resin, the curing agent and the flame retardant are in a liquid state and some are in a solid state. The solid is dissolved first, so that the dissolution degree of the solid is convenient to observe.
According to an aspect of the present invention, if the halogen-free resin composition includes a solid curing agent and a solid epoxy resin, the method of mixing the epoxy resin in the halogen-free resin composition and the solid component in the curing agent with a partial solvent and stirring to completely dissolve the solid in the solvent comprises: firstly, the solid component in the curing agent is dissolved, and then the solid component in the epoxy resin is dissolved. Because the viscosity of the epoxy resin is relatively high, if the epoxy resin is dissolved together with the curing agent, whether the curing agent is completely dissolved is not easy to distinguish.
According to one aspect of the invention, the order of adding the liquid components is: epoxy resin, a curing agent A, a curing agent B, a flame retardant, a curing accelerator and a coupling agent.
According to one aspect of the present invention, the gel time of the halogen-free resin composition obtained by mixing is 250-300 s.
The invention also provides a prepreg, which comprises glass fiber cloth and the halogen-free resin composition attached to the surface and the lines of the glass fiber cloth.
According to one aspect of the invention, the thickness of the prepreg is 0.18 to 0.24mm, preferably 0.20 to 0.22 mm.
The halogen-free resin composition contains the organic phosphorus curing agent, has good wetting property, and can be immersed into the lines of the glass fiber cloth to ensure that the surface of the prepreg is smooth.
The invention also provides a preparation method of the prepreg, which comprises the following steps:
preparing a halogen-free resin composition by using the preparation method of the halogen-free resin composition;
and (3) soaking the glass fiber cloth in the halogen-free resin composition, and baking to obtain a prepreg.
According to one aspect of the invention, the temperature of the baking is 150-.
According to one aspect of the invention, the baking time is 3-8 min.
The invention also provides a laminated board which comprises two metal foils and the prepreg sandwiched between the two metal foils.
According to an aspect of the present invention, the number of the prepregs is one or two or more, and when the number of the prepregs is two or more, the prepregs have a laminated structure.
According to one aspect of the invention, the metal foil is a copper foil.
According to one aspect of the invention, the thickness of the metal foil is 12-105 μm, preferably 18-70 μm, and more preferably 35 μm.
The invention also provides a preparation method of the laminated plate, which comprises the following steps:
preparing a prepreg by adopting the preparation method of the prepreg;
stacking two metal foils on the upper surface and the lower surface of a prepreg; and
and laminating the metal foil and the prepreg to obtain the laminated board.
According to one aspect of the invention, the lamination is performed in a vacuum environment.
According to one aspect of the invention, the heating rate of the lamination is 1.1-2.5 ℃/min.
According to an aspect of the invention, the maximum pressure is applied to the metal foil and the prepreg when the temperature of the prepreg reaches 90-120 ℃.
Preferably, the maximum pressure is 350-.
According to one aspect of the invention, the temperature of the prepreg is controlled at 195-210 ℃ and the temperature is kept for 90-140min during curing.
The lamination process is to melt and then cure the resin. And the pressure of the semi-solidified sheet and the metal foil is increased in a step-type manner. The maximum pressure is applied to the metal foil and the prepreg one third to one half of the maximum pressure before the temperature reaches 90 c, and the maximum pressure is applied when the temperature reaches 90-120 c. The applied pressure needs to be strictly controlled, and if the maximum pressure is applied prematurely, the resin in the prepreg can be lost due to the excessive pressure; if the maximum pressure is applied too late, the resin in the prepreg is easily cured, and the resin in the prepreg has poor fluidity, which may cause defects in the finally prepared laminate.
The invention has the beneficial effects that:
1. the halogen-free resin composition does not contain halogen, and according to the synergistic effect of the epoxy resin, the phosphorus element, the inorganic filler and the flame retardant, the epoxy resin provides a carbon source, the phosphorus element provides an acid source, and the nitrogen element provides a gas source for synergistic flame retardance. The inorganic filler is heated to decompose water vapor and oxides, the concentration of combustible gas and oxygen is reduced while the temperature is reduced, the decomposed oxides can adsorb particles and reduce smoke density, low-smoke halogen-free flame retardance is realized, and the flame retardance reaches UL 94V-0 grade.
2. The novel organic phosphine curing agent with the micromolecule structure with good heat resistance replaces a substance containing a DOPO structure, the organic phosphine curing agent can perform a curing reaction with epoxy resin, the steric hindrance of the molecular structure is small, the halogen-free resin composition has good wettability, the surface of the prepared prepreg is flat and smooth, and the processing operation window is improved; the laminated board has the advantages of few surface appearance defects, high dimensional stability and excellent electrical insulation performance, and can meet the high standards and high requirements of high-performance printed circuit boards on the processing fineness and the circuit accuracy.
3. The phenolic resin curing agent is selected to enable the epoxy resin composition to have excellent moist heat resistance and heat resistance.
4. The addition of more inorganic filler gives epoxy resin compositions having a low coefficient of expansion.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a pictorial representation of a prepreg according to example 1B;
FIG. 2 is a schematic representation of a prepreg according to example 2B;
FIG. 3 is a pictorial view of a prepreg according to example 3B;
FIG. 4 is a pictorial view of a prepreg according to example 4B;
FIG. 5 is a pictorial view of a prepreg according to example 5B;
fig. 6 is a physical diagram of a prepreg of comparative example 6B.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1A:
this example shows a method for preparing a halogen-free resin composition, which specifically comprises the following steps:
step 1): weighing the following raw material components in parts by weight:
313g of an epoxy resin (including 45g of a dicyclopentadiene epoxy resin, 160g of a phosphorus-containing novolac epoxy resin having a solid content of 70%, 100g of an isocyanate-type epoxy resin having a solid content of 75% and 8g of a tetrafunctional epoxy resin having a solid content of 70%, the components other than the solid content being a solvent),
42g of curing agent A (comprising 1.5g of dicyandiamide and 40.5g of bisphenol A type phenol resin),
15g of curing agent B (15 g of organic phosphorus curing agent is adopted),
140g of an inorganic filler (comprising 100g of aluminum hydroxide and 40g of silica),
0.31g of a curing accelerator (0.31 g of 2-methylimidazole was used),
1g of coupling agent (1 g of silane coupling agent is used),
160g of solvent (comprising 140g of propylene glycol methyl ether and 20g of butanone).
Step 2): adding dicyandiamide, bisphenol A type phenolic resin and propylene glycol methyl ether into a mixing bottle, and stirring to completely dissolve dicyandiamide and bisphenol A type phenolic resin in propylene glycol methyl ether.
Step 3): adding the dicyclopentadiene epoxy resin into a mixing bottle, and stirring to dissolve the dicyclopentadiene epoxy resin; then sequentially adding the phosphorus-containing novolac epoxy resin, the isocyanate type epoxy resin, the tetrafunctional epoxy resin, the organic phosphorus curing agent, the 2-methylimidazole and the silane coupling agent into the glue mixing bottle, and stirring until the materials are uniformly mixed.
Step 4): adding aluminum hydroxide, silicon dioxide and butanone into the glue mixing bottle, and stirring until the mixture is uniformly mixed to obtain the halogen-free resin composition.
Example 1B:
the embodiment shows a preparation process for preparing a prepreg by using the method of embodiment 1A, which specifically comprises the following steps:
step 1): a halogen-free resin composition was prepared by the method of example 1A.
Step 2): the glass fiber cloth was immersed in the halogen-free resin composition and baked in an oven at 170 ℃ for 6 minutes to obtain a prepreg having a smooth surface as shown in fig. 1.
Example 1C:
this example illustrates the preparation of a laminate using the method of example 1B, using the following steps:
step 1): 6 prepregs were prepared using the method of example 1B.
Step 2): 6 prepregs were stacked up in order and 35 μm copper foil was coated on both sides.
Step 3): placing the copper foil and the prepreg in a vacuum hot oil press for laminating, wherein the heating rate of the laminating is 1.5 ℃/min; applying a maximum pressure of 400psi when the temperature of the prepreg reaches 100 ℃; and during curing, controlling the temperature of the prepreg at 205 ℃, and preserving the heat for 120min to obtain the laminated board. The properties of the laminate are shown in table 1.
Example 2A:
this example shows a method for preparing a halogen-free resin composition, which specifically comprises the following steps:
step 1): weighing the following raw material components in parts by weight:
335g of epoxy resin (including 151g of bisphenol A type novolac epoxy resin, 70g of phosphorus-containing novolac epoxy resin with a solid content of 70%, 110g of isocyanate type epoxy resin with a solid content of 75% and 4g of tetrafunctional epoxy resin with a solid content of 70%, the components except the solid content being solvents),
curing agent A41.2 g (comprising 1.2g dicyandiamide and 40g phenolic novolac resin),
26g of curing agent B (26 g of organic phosphorus curing agent is adopted),
142g of an inorganic filler (including 95g of aluminum hydroxide and 47g of magnesium hydroxide),
0.58g of a curing accelerator (0.58 g of 2-phenylimidazole was used),
0.92g of a coupling agent (0.92 g of a silane coupling agent was used),
190g of solvent (including 165g of propylene glycol methyl ether and 25g of butanone).
Step 2): adding dicyandiamide, linear phenolic resin and propylene glycol methyl ether into a mixing bottle, and stirring to completely dissolve dicyandiamide and linear phenolic resin in propylene glycol methyl ether.
Step 3): adding the bisphenol A epoxy resin into a mixing bottle, and stirring to dissolve the bisphenol A epoxy resin; then sequentially adding the phosphorus-containing novolac epoxy resin, the isocyanate type epoxy resin, the tetrafunctional epoxy resin, the organic phosphorus curing agent, the 2-phenylimidazole and the silane coupling agent into the glue mixing bottle, and stirring until the mixture is uniformly mixed.
Step 4): adding aluminum hydroxide, magnesium hydroxide and butanone into the glue mixing bottle, and stirring until uniform mixing is achieved to obtain the halogen-free resin composition.
Example 2B:
the embodiment shows a preparation process for preparing a prepreg by using the method of embodiment 2A, which specifically comprises the following steps:
step 1): a halogen-free resin composition was prepared by the method of example 2A.
Step 2): the glass fiber cloth was immersed in the halogen-free resin composition and baked in an oven at 175 ℃ for 4 minutes to obtain a prepreg having a smooth surface as shown in fig. 2.
Example 2C:
this example illustrates the process of making a laminate using the method of example 2B, with the following steps:
step 1): 5 sheets of prepreg were prepared using the method of example 2B.
Step 2): 5 prepregs were stacked up in order and 35 μm copper foil was coated on both sides.
Step 3): placing the copper foil and the prepreg in a vacuum hot oil press for laminating, wherein the heating rate of the laminating is 2.5 ℃/min; applying a maximum pressure of 350psi when the temperature of the prepreg reaches 120 ℃; and during curing, controlling the temperature of the prepreg at 210 ℃, and preserving the heat for 90min to obtain the laminated board. The properties of the laminate are shown in table 1.
Example 3A:
this example shows a method for preparing a halogen-free resin composition, which specifically comprises the following steps:
step 1): weighing the following raw material components in parts by weight:
356g of an epoxy resin (comprising 60g of a dicyclopentadiene epoxy resin, 120g of a novolac epoxy resin, 170 g of an isocyanate-type epoxy resin having a solid content of 75% and 5g of a tetrafunctional epoxy resin having a solid content of 70%, the components other than the solid content being solvents),
66.3g of curing agent A (comprising 1.3g of diaminodiphenyl sulfone, 10g of bisphenol A type phenolic resin and 55g of 56% solid content phosphorus-containing phenolic resin, the components except the solid content are solvents),
15g of curing agent B (15 g of organic phosphorus curing agent is adopted),
144g of inorganic filler (144 g of aluminum hydroxide is adopted),
4g of flame retardant (4 g of polycondensation type phosphate ester is adopted),
0.53g of a curing accelerator (0.53 g of 2-ethyl-4-methylimidazole was used),
1.2g of a coupling agent (1.2 g of a silane coupling agent was used),
175g of a solvent (comprising 160g of propylene glycol methyl ether acetate and 15g of butanone).
Step 2): adding the diaminodiphenyl sulfone, the bisphenol A type phenolic resin and the propylene glycol monomethyl ether acetate into a mixing bottle, and stirring to completely dissolve the diaminodiphenyl sulfone and the bisphenol A type phenolic resin in the propylene glycol monomethyl ether acetate.
Step 3): adding dicyclopentadiene epoxy resin and linear phenolic epoxy resin into a glue mixing bottle, and stirring to dissolve the dicyclopentadiene epoxy resin and the linear phenolic epoxy resin; then adding isocyanate type epoxy resin, tetrafunctional epoxy resin, phosphorus-containing phenolic resin, organic phosphorus curing agent, polycondensation type phosphate ester, 2-ethyl-4-methylimidazole and silane coupling agent into the glue mixing bottle in sequence, and stirring until the materials are uniformly mixed.
Step 4): and adding aluminum hydroxide and butanone into the glue mixing bottle, and stirring until the mixture is uniformly mixed to obtain the halogen-free resin composition.
Example 3B:
the embodiment shows a preparation process for preparing a prepreg by using the method of embodiment 3A, which specifically comprises the following steps:
step 1): a halogen-free resin composition was prepared by the method of example 3A.
Step 2): the glass fiber cloth was immersed in the halogen-free resin composition and baked in an oven at 160 ℃ for 8 minutes to obtain a prepreg having a smooth surface as shown in fig. 3.
Example 3C:
this example illustrates the preparation of a laminate using the method of example 3B, using the following steps:
step 1): 4 prepregs were prepared using the method of example 3B.
Step 2): 4 prepregs were stacked up in order and 35 μm copper foil was coated on both sides.
Step 3): placing the copper foil and the prepreg in a vacuum hot oil press for laminating, wherein the heating rate of the laminating is 1.1 ℃/min; applying a maximum pressure of 450psi when the temperature of the prepreg reaches 90 ℃; and (3) during curing, controlling the temperature of the prepreg at 195 ℃, and preserving the heat for 140min to obtain the laminated board. The properties of the laminate are shown in table 1.
Example 4A:
this example shows a method for preparing a halogen-free resin composition, which specifically comprises the following steps:
step 1): weighing the following raw material components in parts by weight:
342g of epoxy resin (comprising 145g of o-methyl novolac epoxy resin, 190g of isocyanate type epoxy resin with 75% solid content and 7g of tetrafunctional epoxy resin with 70% solid content, and the components except the solid content are solvents),
curing agent A51.8 g (including 2.5g diaminodiphenylmethane, 39.3g phenol-formaldehyde novolac resin and 10g phosphorus-containing phenol-formaldehyde resin with 56% solid content, the components except the solid content are solvent),
26g of curing agent B (26 g of organic phosphorus curing agent is adopted),
136g of inorganic filler (including 102g of magnesium hydroxide and 34g of mica powder),
flame retardant 6.5g (using 6.5g phosphazene)
0.78g of a curing accelerator (0.52 g of 2-ethyl-4-methylimidazole and 0.26g of aluminum acetylacetonate),
1.14g of a coupling agent (1.14 g of a silane coupling agent was used),
168g of solvent (comprising 150g of propylene glycol methyl ether acetate and 18g of cyclohexanone).
Step 2): adding the diaminodiphenylmethane, the linear phenolic resin and the propylene glycol monomethyl ether acetate into a glue mixing bottle, and stirring to completely dissolve the diaminodiphenylmethane and the linear phenolic resin in the propylene glycol monomethyl ether acetate.
Step 3): adding o-methyl novolac epoxy resin into a glue mixing bottle, and stirring to dissolve the o-methyl novolac epoxy resin; then adding isocyanate type epoxy resin, tetrafunctional epoxy resin, phosphorus-containing phenolic resin, organic phosphorus curing agent, 2-ethyl-4-methylimidazole, aluminum acetylacetonate and silane coupling agent into the glue mixing bottle in sequence, and stirring until the materials are uniformly mixed.
Step 4): and adding the phosphazene, the magnesium hydroxide, the mica powder and the cyclohexanone into the rubber mixing bottle, and stirring until the materials are uniformly mixed to obtain the halogen-free resin composition.
Example 4B:
the embodiment shows a preparation process for preparing a prepreg by using the method of embodiment 4A, which specifically comprises the following steps:
step 1): a halogen-free resin composition was prepared by the method of example 4A.
Step 2): the glass fiber cloth was immersed in the halogen-free resin composition and baked in an oven at 180 ℃ for 3 minutes to obtain a prepreg having a smooth surface as shown in fig. 4.
Example 4C:
this example illustrates the preparation of a laminate using the method of example 4B, using the following steps:
step 1): 6 prepregs were prepared using the method of example 4B.
Step 2): 6 prepregs were stacked up in order and 35 μm copper foil was coated on both sides.
Step 3): placing the copper foil and the prepreg in a vacuum hot oil press for laminating, wherein the heating rate of the laminating is 2 ℃/min; applying a maximum pressure of 420psi when the temperature of the prepreg reaches 110 ℃; and during curing, controlling the temperature of the prepreg at 200 ℃, and preserving the heat for 120min to obtain the laminated board. The properties of the laminate are shown in table 1.
Example 5A (most preferred example):
this example shows a method for preparing a halogen-free resin composition, which specifically comprises the following steps:
step 1): weighing the following raw material components in parts by weight:
354g of an epoxy resin (including 138g of a biphenyl type epoxy resin, 216g of a 75% solid content isocyanate type epoxy resin, and the components other than the solid content were solvents),
41g of curing agent A (41 g of diaminodiphenyl sulfone is adopted),
29g of curing agent B (29 g of organic phosphorus curing agent),
182g of inorganic filler (comprising 154g of aluminum hydroxide and 28g of kaolin),
flame retardant 10g (10 g of triphenyl phosphate is used)
0.45g of a curing accelerator (0.45 g of 2-methylimidazole was used),
1.5g of a coupling agent (1.5 g of a silane coupling agent was used),
190g of solvent (including 178g of dimethylformamide and 12g of acetone).
Step 2): adding the diamino diphenyl sulfone and the dimethyl formamide into a mixing bottle, and stirring to completely dissolve the diamino diphenyl sulfone in the dimethyl formamide.
Step 3): adding biphenyl epoxy resin into a mixing bottle, and stirring to dissolve the ortho-biphenyl epoxy resin; then adding isocyanate type epoxy resin, an organic phosphorus curing agent, triphenyl phosphate, 2-methylimidazole and a silane coupling agent into the glue mixing bottle in sequence, and stirring until the materials are uniformly mixed.
Step 4): adding aluminum hydroxide, kaolin and cyclohexanone into the rubber mixing bottle, and stirring until the mixture is uniformly mixed to obtain the halogen-free resin composition.
Example 5B:
this example shows a preparation process for preparing a prepreg using the method of example 5A, specifically including the steps of:
step 1): a halogen-free resin composition was prepared by the method of example 5A.
Step 2): the glass fiber cloth was immersed in the halogen-free resin composition and baked in an oven at 175 ℃ for 6 minutes to obtain a prepreg having a smooth surface as shown in fig. 5.
Example 5C:
this example illustrates the preparation of a laminate using the method of example 5B, using the following steps:
step 1): 5 sheets of prepreg were prepared using the method of example 5B.
Step 2): 5 prepregs were stacked up in order and 35 μm copper foil was coated on both sides.
Step 3): placing the copper foil and the prepreg in a vacuum hot oil press for laminating, wherein the heating rate of the laminating is 1.5 ℃/min; applying a maximum pressure of 400psi when the temperature of the prepreg reaches 110 ℃; and during curing, controlling the temperature of the prepreg at 205 ℃, and preserving the heat for 120min to obtain the laminated board. The properties of the laminate are shown in table 1.
Comparative example 6A:
the comparative example shows a preparation method of a halogen-free resin composition with a conventional formula, which specifically comprises the following steps:
step 1): weighing the following raw material components in parts by weight:
374g of an epoxy resin (including 30g of a novolac epoxy resin, 120g of a phosphorus-containing novolac epoxy resin having a solid content of 70%, 220g of an isocyanate-type epoxy resin having a solid content of 75% and 4g of a polyfunctional epoxy resin having a solid content of 70%, the components other than the solid content being solvents),
95.5g of a curing agent (2.5 g of dicyandiamide, 28g of bisphenol A type phenolic resin and 65g of 56% solid content phosphorus-containing phenolic resin, and components except the solid content are solvents),
180g of an inorganic filler (comprising 128g of aluminum hydroxide and 52g of silica),
0.36g of a curing accelerator (0.36 g of 2-ethyl-4-methylimidazole was used),
1.4g of a coupling agent (1.4 g of a silane coupling agent was used),
195g of solvent (comprising 175g of propylene glycol methyl ether and 20g of butanone).
Step 2): adding dicyandiamide, bisphenol A type phenolic resin and propylene glycol methyl ether into a mixing bottle, and stirring to completely dissolve dicyandiamide and bisphenol A type phenolic resin in propylene glycol methyl ether.
Step 3): adding the linear phenolic epoxy resin into a glue mixing bottle, and stirring to dissolve the linear phenolic epoxy resin; then adding the phosphorus-containing phenolic epoxy resin, the isocyanate type epoxy resin, the multifunctional epoxy resin, the phosphorus-containing phenolic resin, the 2-ethyl-4-methylimidazole and the silane coupling agent into the glue mixing bottle in sequence, and stirring until the materials are uniformly mixed.
Step 4): adding aluminum hydroxide, silicon dioxide and cyclohexanone into the rubber mixing bottle, and stirring until the mixture is uniformly mixed to obtain the halogen-free resin composition.
Comparative example 6B:
the present comparative example shows a preparation process for preparing a prepreg using the method of comparative example 6A, specifically employing the following steps:
step 1): the halogen-free resin composition was prepared by the method of comparative example 6A.
Step 2): the glass fiber cloth was immersed in the halogen-free resin composition and baked in an oven at 175 ℃ for 4 minutes to obtain a prepreg as shown in fig. 6. It can be seen that the prepreg of fig. 6 has a rough surface, and the glass fiber cloth has a very marked texture, which may show insufficient wettability.
Comparative example 6C:
this comparative example shows a process for making a laminate using the method of comparative example 6B, using the following steps:
step 1): 5 sheets of prepreg were prepared using the method of comparative example 6B.
Step 2): 5 prepregs were stacked up in order and 35 μm copper foil was coated on both sides.
Step 3): placing the copper foil and the prepreg in a vacuum hot oil press for laminating, wherein the heating rate of the laminating is 2.5 ℃/min; applying a maximum pressure of 350psi when the temperature of the prepreg reaches 120 ℃; and during curing, controlling the temperature of the prepreg at 210 ℃, and preserving the heat for 90min to obtain the laminated board. The properties of the laminate are shown in table 1.
Figure BDA0002218954600000181
TABLE 1 Properties of copper clad laminates of examples 1 to 5 and comparative example 6
Table 1 the respective performance test methods are as follows:
peel strength: the peel strength of the metal overlay was tested under "normal" test conditions as in IPC-TM-650 test method 2.4.8.
Thermal shock: the delamination time of the floating tin in a tin furnace at 288 ℃ was examined according to IPC-TM-650 test method 2.4.13.1.
Glass transition temperature: the tests were carried out according to the DSC method specified in IPC-TM-650 test method 3.4.25.
Thermal expansion coefficient of Z axis: the coefficient of expansion in the Z-axis (Z-CTE) is measured as specified by IPC-TM-650 test method 2.4.24 for TMA at temperatures from 50 ℃ to 250 ℃.
Breakdown strength: the test was conducted according to the puncture strength method specified in IPC-TM-650 test method 2.5.6.2.
Breakdown voltage: the test was performed according to the breakdown voltage method specified in IPC-TM-650 test method 2.5.6.
Flame retardancy: the test was carried out according to UL 94.
Moisture and heat resistance: the time for delamination and foaming in a tin furnace at 288 ℃ after the autoclave cooking test (PCT) was investigated according to IPC-TM-650 test method 2.6.16.
As can be seen from fig. 1 to 5, in the compositions of examples 1 to 5, the amount of DOPO structure-containing material was smaller and smaller, and therefore prepregs were produced to be smoother and smoother. Comparative example 6 contains a large amount of DOPO structure and does not contain curing agent B, so the appearance of the prepreg is the roughest.
As shown in Table 1, the halogen-free resin composition, the prepreg and the laminated board prepared by the invention can realize halogen-free flame retardance. The halogen-free resin composition has good wettability in glass fiber cloth, and the surface of the prepreg is flat and smooth. The copper-clad laminate has excellent moisture and heat resistance, has low expansion coefficient, has less open circuit and short circuit defects generated in the subsequent circuit board processing process, such as drilling, copper deposition, electroplating and other process processes, can meet the high standard and high requirement of high-performance printed circuit boards on the processing fineness and the circuit accuracy, and has wide application prospect.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A halogen-free resin composition is characterized by comprising the following components:
the weight portions are as follows:
300 portions and 400 portions of epoxy resin,
40-70 parts of a curing agent A,
10-30 parts of a curing agent B,
130 portions and 200 portions of inorganic filler,
0.1 to 0.8 portion of curing accelerator,
0.7 to 1.5 portions of coupling agent,
150 portions of 225 portions of solvent,
wherein, the content of the components except the solvent is 60 to 75 percent.
2. The halogen-free resin composition according to claim 1,
comprises the following components:
the weight portions are as follows:
354 parts of epoxy resin, namely 354 parts of epoxy resin,
41 parts of a curing agent A, namely,
29 parts of a curing agent B, namely,
182 parts of an inorganic filler, namely an inorganic filler,
0.45 part of a curing accelerator,
1.5 parts of a coupling agent,
224 parts of a solvent, namely 224 parts of,
wherein, the content of the components except the solvent is 60 to 75 percent;
preferably, the epoxy resin includes one or a combination of two or more of bisphenol a type epoxy resin, phenol novolac type epoxy resin, bisphenol a phenol novolac type epoxy resin, o-methyl phenol novolac type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, isocyanate type epoxy resin, tetrafunctional epoxy resin, or phosphorus-containing phenol novolac epoxy resin; further preferably, the phosphorus-containing novolac epoxy resin comprises one or a combination of more than two of DOPO modified novolac epoxy resin, DOPO-HQ modified novolac epoxy resin or DOPO-NQ modified novolac epoxy resin;
preferably, the curing agent A comprises one or a combination of more than two of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, p-xylidine, dicyandiamide, phenol-formaldehyde novolac resin, bisphenol A type phenol-formaldehyde resin or phosphorus-containing phenol-formaldehyde resin; further preferably, the phosphorus-containing phenolic resin comprises one or more of DOPO modified phenolic resin, DOPO-HQ modified phenolic resin or DOPO-NQ modified phenolic resin;
preferably, the curing agent B is an organic phosphorus curing agent, and the structural formula of the curing agent B is as follows:
Figure FDA0002218954590000021
wherein R1 is an aliphatic group, R2 is an aliphatic group;
preferably, the inorganic filler comprises one or a combination of more than two of silica, magnesium hydroxide, mica powder, kaolin, talcum powder, calcium carbonate or aluminum hydroxide; preferably, the inorganic filler is an inorganic filler subjected to surface treatment by a silane coupling agent;
preferably, the halogen-free resin composition further comprises a flame retardant, wherein the weight part of the flame retardant is less than 20 parts, preferably less than 10 parts; preferably, the flame retardant comprises one or the combination of more than two of triphenyl phosphate, ammonium polyphosphate, condensed phosphate, phosphazene, aluminum hypophosphite, aluminum diethylphosphinate, melamine polyphosphate or melamine cyanurate;
preferably, the curing accelerator comprises an imidazole accelerator and/or an organometallic salt; further preferably, the imidazole-based accelerator comprises 2-ethyl-4-methylimidazole or 2-methylimidazole; further preferably, the organometallic salt comprises aluminum acetylacetonate or cobalt acetylacetonate;
preferably, the coupling agent is a silane coupling agent;
preferably, the solvent comprises one or a combination of more than two of acetone, butanone, dimethylformamide, propylene glycol methyl ether acetate or cyclohexanone.
3. A method for preparing a halogen-free resin composition, characterized in that the halogen-free resin composition according to any of claims 1-3 is used, comprising the steps of:
mixing the solid components in the epoxy resin and the curing agent in the halogen-free resin composition with a part of solvent, and stirring to completely dissolve the solid components in the solvent;
adding the liquid components, and stirring until the liquid components are uniformly mixed; and
adding the solid flame retardant, the inorganic filler and the residual solvent, and stirring until the mixture is uniformly mixed to obtain the halogen-free resin composition;
preferably, if the halogen-free resin composition comprises a solid curing agent and a solid epoxy resin, the method of mixing the epoxy resin in the halogen-free resin composition and the solid component in the curing agent with a part of the solvent and stirring to completely dissolve the solid component in the solvent comprises: firstly, the solid component in the curing agent is dissolved, and then the solid component in the epoxy resin is dissolved.
Preferably, the order of addition of the liquid components is: epoxy resin, a curing agent A, a curing agent B, a flame retardant, a curing accelerator and a coupling agent;
preferably, the gel time of the halogen-free resin composition obtained by mixing is 250-300 s.
4. A prepreg comprising a glass cloth, the halogen-free resin composition according to claim 1 or 2 attached to the surface of the glass cloth and the grain of the glass cloth;
preferably, the thickness of the prepreg is 0.18 to 0.24mm, preferably 0.20 to 0.22 mm.
5. The preparation method of the prepreg is characterized by comprising the following steps:
preparing a halogen-free resin composition using the method of claim 3;
and (3) soaking the glass fiber cloth in the halogen-free resin composition, and baking to obtain a prepreg.
6. The method for preparing a prepreg according to claim 5, wherein the baking temperature is 150-180 ℃;
preferably, the baking time is 3-8 min.
7. A laminate comprising two metal foils and the prepreg according to claim 4 sandwiched between the two metal foils.
8. The laminate of claim 7, wherein the prepreg is one or more than two sheets, and when the prepreg is two or more than two sheets, the prepreg has a laminated structure;
preferably, the metal foil is a copper foil;
preferably, the thickness of the metal foil is 12-105 μm, preferably 18-70 μm, further preferably 35 μm.
9. A method of making a laminate, comprising the steps of:
preparing a prepreg using the method according to claim 5 or 6;
stacking two metal foils on the upper surface and the lower surface of a prepreg; and
and laminating the metal foil and the prepreg to obtain the laminated board.
10. The method of making the laminate of claim 9, wherein the lamination is performed in a vacuum environment;
preferably, the heating rate of the lamination is 1.1-2.5 ℃/min;
preferably, the maximum pressure is applied to the metal foil and the prepreg when the temperature of the prepreg reaches 90 to 120 ℃; further preferably, the maximum pressure is 350-;
preferably, the temperature of the prepreg is controlled at 195-210 ℃ during curing, and the temperature is kept for 90-140 min.
CN201910926060.9A 2019-09-27 2019-09-27 Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof Active CN110655757B (en)

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CN113844130A (en) * 2021-09-13 2021-12-28 山东金宝电子股份有限公司 Preparation method of high-Tg high-frequency copper-clad plate
CN115011295A (en) * 2022-06-29 2022-09-06 江西省宏瑞兴科技股份有限公司 Halogen-free adhesive for manufacturing copper clad laminate and preparation method thereof
CN115044171A (en) * 2022-06-30 2022-09-13 浙江华正新材料股份有限公司 Resin composition, resin-based composite material and preparation method thereof

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CN109504038A (en) * 2018-12-11 2019-03-22 广州联茂电子科技有限公司 A kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate

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