CN117986801B - Low dielectric resin composition and application thereof - Google Patents

Abstract

The present invention relates to a low dielectric resin composition and its application, and relates to the field of new materials. The low dielectric resin composition includes an initiator, a soft resin, a hard resin, a cross-linking agent, 3-(methacryloyloxy)propyltrimethoxysilane and an inorganic filler; the initiator has a benzene ring structure; the soft resin includes a hydrocarbon resin and/or a polystyrene resin, and the hard resin includes a polyphenylene ether with vinyl groups at both ends; the cross-linking agent includes a compound with a styrene structure. The film material prepared using the low dielectric resin composition has a low dielectric constant and a low dielectric loss, and can give the film material appropriate rollability so that it can be stored in the form of a roll.

Description

Low dielectric resin composition and application thereof

Technical Field

The invention relates to the field of new materials, in particular to a low dielectric resin composition and application thereof.

Background

With the rapid development of the fifth generation mobile communication technology (abbreviated as 5G), the requirements on the transmission speed and the signal quality of the communication are increasing, and the industry starts to research the film material with lower dielectric constant (Dk) and lower dielectric loss (Df), so that it is desired to prepare the packaging material or the build-up material of the wafer by using the film material, thereby meeting the requirements on the transmission speed and the signal quality of the 5G technology.

Meanwhile, besides higher requirements on dielectric constant and dielectric loss, the requirements on flexibility of the film material are also increased increasingly, and the film material used as a wafer packaging material or a build-up material in the past has the condition of hard and brittle properties, so that the problem that an operator is easy to crack the film material when attaching the wafer with the film material is solved. Moreover, when the film material is brittle and hard, the film material cannot be rolled up and stored in the form of coiled materials, so that manufacturers need to put a large space for storing the film material.

Therefore, how to make the film material have lower dielectric constant and electric loss and moderate hardness, so that the film material can be better suitable for packaging materials or build-up materials of wafers, and has proper coiling property, so that the film material can be stored in a coiled material form, which is a difficult problem to be overcome at present.

Disclosure of Invention

In view of the above-described problems, the present invention provides a low dielectric resin composition, and a film material prepared from the low dielectric resin composition has a low dielectric constant and low dielectric loss, and can impart suitable coiling properties to the film material, so that the film material can be stored in a roll form.

In order to achieve the above object, the present invention provides a low dielectric resin composition comprising the following raw materials: initiator, soft resin, hard resin, cross-linking agent, 3- (methacryloxy) propyl trimethoxy silane and inorganic filler;

the mass percentages of the raw materials are as follows:

3wt% or less of initiator 10wt%,5wt% or less of soft resin 20wt%,2wt% or less of hard resin 15wt%,5wt% or less of cross-linking agent 20wt%,0wt% or less of 3- (methacryloyloxy) propyl trimethoxysilane 3wt% or less, and 55wt% or less of inorganic filler 75wt% or less;

The initiator has a benzene ring structure; the soft resin is thermoplastic resin, and comprises hydrocarbon resin and/or polystyrene resin; the hard resin is thermosetting resin, and comprises polyphenyl ether with vinyl groups at two ends; the crosslinking agent includes a compound having a styrene structure.

The low dielectric array composition obtained by compounding the raw materials with the structure and the dosage can be used for preparing the low dielectric film with low dielectric constant of less than 2.9 and low dielectric loss value of less than 0.0029 at the frequency of 10GHz, and the low dielectric film has good coiling property and can be stored in a coiled material form.

The initiator having a benzene ring structure is a radical initiator, and can convert the double bond structure in the crosslinking agent into a radical, and further, the crosslinking agent having the radical, the soft resin and the hard resin undergo polymerization reaction to form a copolymer. In order to enable the initiator to generate enough free radicals and further enable the soft resin, the hard resin and the cross-linking agent to form better reactivity, the amount of the initiator with the benzene ring structure is more than or equal to 3wt%, and meanwhile, in order to avoid the situation that the initiator generates excessive free radicals to cause the polymerization reaction with the cross-linking agent with the free radicals after preliminary reaction or cause the polymerization reaction with the soft resin and the hard resin to cause the poor reactivity among the cross-linking agent, the soft resin and the hard resin, the amount of the initiator with the benzene ring structure is less than or equal to 10wt%.

The soft resin and the hard resin are matched, so that the film material has proper soft hardness and good film forming property, and has good coiling property. It will be appreciated that the above rollability means that the film can be rolled up and stored in roll form. In order to prevent the film from being too hard and brittle to cause no rolling, the dosage of the soft resin is more than or equal to 5wt percent, and the dosage of the hard resin is less than or equal to 15wt percent; meanwhile, in order to prevent the film from being too soft and broken easily due to pulling in the process of being attached to the wafer, the using amount of the soft resin is less than or equal to 20wt% and the using amount of the hard resin is more than or equal to 2wt%.

In order to enable the film material to have proper thermal expansion coefficient and proper glass transition temperature, the usage amount of the cross-linking agent with the styrene structure is more than or equal to 5wt percent, and meanwhile, in order to enable the film material to be formed with higher cross-linking density in the subsequent curing reaction process of the low dielectric resin composition, the usage amount of the cross-linking agent is less than or equal to 20wt percent.

The 3- (methacryloyloxy) propyltrimethoxysilane is used as a silane coupling agent, and because the component has the characteristic of low polarity, the component is favorable for compounding with other raw materials, and the film material has a dielectric constant of less than 2.9 and a dielectric loss value of less than 0.0029 at a frequency of 10 GHz. Meanwhile, in order to enable the inorganic filler to be uniformly dispersed to form a colloid solution in the subsequent process of preparing the membrane material, the dosage of the 3- (methacryloyloxy) propyl trimethoxysilane is more than 0wt%; meanwhile, in order to avoid the release force between the film material and the light release film which are obtained by subsequent preparation and the release force between the film material and the heavy release film being relatively close, or in order to avoid the phenomenon of counter release between the film material and the light release film and the heavy release film which are obtained by subsequent preparation, the use amount of the 3- (methacryloyloxy) propyl trimethoxy silane is less than or equal to 3wt percent, so as to ensure the preservation property of the film material and be beneficial to subsequent use.

In order to make the film material have good film forming property, proper thermal expansion coefficient and proper glass transition temperature, inorganic filler is introduced into the formula, and the type of the inorganic filler is not particularly limited, so long as the low dielectric film has good film forming property, proper thermal expansion coefficient and proper glass transition temperature. In order to make the low dielectric film have proper thermal expansion coefficient and proper glass transition temperature, the amount of the inorganic filler is more than or equal to 55wt%; meanwhile, in order to ensure that the film material can completely cover the circuit on the copper foil substrate without gaps when the film material is attached to the surface of the copper foil substrate by the subsequent vacuum attaching treatment, the using amount of the inorganic filler is less than or equal to 75wt%.

In one embodiment, the hydrocarbon resin comprises a Denka LDM-02-A model hydrocarbon resin.

In one embodiment, the initiator is present in an amount of 4 to 9 weight percent.

By adopting the initiator with the dosage, the cross-linking agent, soft resin and hard resin have better reactivity.

In one embodiment, the initiator is present in an amount of 4 to 8 weight percent.

In one embodiment, the soft resin accounts for 50-90wt% of the sum of the soft resin and the hard resin, and the hard resin accounts for 10-50wt% of the sum of the soft resin and the hard resin.

In order to ensure that the film material has better coiling property, the film material is not too hard and brittle, cannot be coiled, is not too soft and is easy to damage due to pulling in the process of being attached to a wafer, and soft resin and hard resin with the mass ratio are adopted.

In one embodiment, the mass of the soft resin is 55-85wt% of the sum of the soft resin and the hard resin.

In one embodiment, the mass of the hard resin is 10-40wt% of the sum of the mass of the soft resin and the mass of the hard resin.

In one embodiment, the soft resin comprises 60-80wt% of the sum of the soft resin and the hard resin.

In one embodiment, the mass of the hard resin is 15-35wt% of the sum of the mass of the soft resin and the mass of the hard resin.

In one embodiment, the crosslinker does not include a compound having a hydroxyl group; the number average molecular weight of the polyphenyl ether with vinyl groups at two ends is 1500g/mol-2500g/mol.

In one embodiment, the initiator comprises dicumyl peroxide; the polystyrene-based resin comprises a styrene-butadiene-styrene block copolymer and/or a hydrogenated styrene-butadiene-styrene block copolymer; the hard resin further comprises polydivinylbenzene and/or divinylbenzene-styrene block copolymers; the compound having a styrene structure includes divinylbenzene.

The hard resin with the specific components can lead the film material to have lower thermal expansion coefficient, higher glass transition temperature, lower dielectric constant and lower dielectric loss value.

In one embodiment, the inorganic filler has an average particle size of > 0.4 μm and a maximum particle size of < 1.0 μm.

It will be appreciated that the maximum particle size mentioned above refers to the minimum standard sieve pore size through which 100% of the filler is required to pass.

The invention also provides a low dielectric film prepared by adopting the low dielectric resin composition through curing reaction.

In one embodiment, the curing reaction comprises the steps of: and mixing the low dielectric resin composition with a dispersing agent to obtain a colloid solution, and performing a curing reaction to obtain the low dielectric film.

The dispersant is not particularly limited as long as it is a dispersant capable of uniformly dispersing the low dielectric resin composition.

In one embodiment, the dispersant is a liquid, and the dispersant includes at least one of a benzene dispersant, a ketone dispersant, and an ester dispersant.

In one embodiment, the dispersant comprises toluene.

The invention also provides application of the low dielectric resin composition or the low dielectric film in wafer packaging and/or build-up.

Compared with the prior art, the invention has the following beneficial effects:

The low dielectric resin composition and the application thereof can be used for preparing a film material with a low dielectric constant of less than 2.9 and a low dielectric loss value of less than 0.0029 at a frequency of 10GHz, and can endow the film material with proper coiling property so as to be stored in a coiled material form.

Detailed Description

In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

The source is as follows:

The reagents, materials and equipment used in the examples are all commercially available sources unless otherwise specified; the test methods are conventional in the art unless otherwise specified.

The reagents and sources of the reagents used in the following examples and comparative examples are shown in the following tables.

Table 1 reagents specifically used in examples and comparative examples

Example 1

A low dielectric resin composition and a low dielectric film.

1. A low dielectric resin composition is prepared.

A low dielectric resin composition was obtained by mixing 5.6% by weight of dicumyl peroxide (initiator), 13.1% by weight of hydrocarbon resin (soft resin), 2.8% by weight of styrene-butadiene-styrene block copolymer (soft resin), 3.7% by weight of polyphenylene ether A having vinyl groups at both ends (hard resin), 13.1% by weight of divinylbenzene (crosslinking agent), 1% by weight of 3-methacryloxypropyl trimethoxysilane (silane coupling agent) and 60.7% by weight of inorganic filler.

2. A low dielectric film is prepared.

The low dielectric resin composition was added to toluene and mixed with zirconium beads to obtain a colloidal solution having a solid content of 50 wt%. The colloidal solution was knife coated on one side surface of a heavy release film using an adjustable film coater (brand: YOSHIMITSU, model: YBA-4), and the heavy release film knife coated with the colloidal solution was placed in an oven set at 110 ℃ for 10 minutes to dry to remove the liquid, thereby curing the colloidal solution and forming a low dielectric film.

And rolling a light release film serving as a protective layer on the surface of the low dielectric film, so that the low dielectric film is clamped between the heavy release film and the light release film to obtain a composite film material.

Example 2

A low dielectric resin composition and a low dielectric film.

Substantially the same as in example 1 was conducted except that: in this example, 5.6% by weight of dicumyl peroxide (initiator), 9.8% by weight of hydrocarbon resin (soft resin), 2.8% by weight of styrene-butadiene-styrene block copolymer (soft resin), 3.7% by weight of polyphenylene ether A having vinyl groups at both ends (hard resin), 3.3% by weight of divinylbenzene-styrene block copolymer (hard resin), 13.1% by weight of divinylbenzene (crosslinking agent), 1% by weight of 3-methacryloxypropyl trimethoxysilane (silane coupling agent) and 60.7% by weight of inorganic filler were mixed to obtain a low dielectric resin composition.

Comparative example 1

Substantially the same as in example 1 was conducted except that: this comparative example uses 5.6wt% of di-t-butyl peroxide as initiator.

Comparative example 2

Substantially the same as in example 1 was conducted except that: this comparative example uses 5.6wt% 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane as an initiator.

Comparative example 3

Substantially the same as in example 1 was conducted except that: this comparative example uses 12.1wt% divinylbenzene and 1wt% dipentaerythritol hexaacrylate as the crosslinking agent.

Comparative example 4

Substantially the same as in example 1 was conducted except that: this comparative example uses 12.1wt% divinylbenzene and 1wt% pentaerythritol tetraacrylate as the crosslinking agent.

Comparative example 5

Substantially the same as in example 1 was conducted except that: this comparative example uses 3.7% by weight of polyphenylene ether B having vinyl groups at both ends as a hard resin.

Comparative example 6

Substantially the same as in example 1 was conducted except that: this comparative example uses 6.6wt% hydrocarbon resin and 2.8wt% styrene-butadiene-styrene block copolymer as soft resin, and 3.7wt% polyphenylene ether A having vinyl groups at both ends and 6.5wt% divinylbenzene-styrene block copolymer as hard resin.

Comparative example 7

Substantially the same as in example 1 was conducted except that: the present comparative example uses 1wt% of vinyltrimethoxysilane as the silane coupling agent.

Comparative example 8

Substantially the same as in example 1 was conducted except that: this comparative example was obtained by mixing 5.6wt% of dicumyl peroxide (initiator), 13.0wt% of hydrocarbon resin (soft resin), 2.8wt% of styrene-butadiene-styrene block copolymer (soft resin), 3.7wt% of polyphenylene ether A having vinyl groups at both ends (hard resin), 13.0wt% of divinylbenzene (crosslinking agent), 0.9wt% of vinyltrimethoxysilane (silane coupling agent), 0.9wt% of 3- (N-anilino) propyltrimethoxysilane (silane coupling agent) and 60.1wt% of inorganic filler.

Experimental example

The films prepared in each example and comparative example were tested.

1. The detection method of the thermal expansion coefficient and the glass transition temperature comprises the following steps: the membrane was measured using a thermo-mechanical analyzer (brand: TA Instruments, model: TMA 450). And heating the membrane material to 260 ℃ to release the stress of the membrane material, and then heating the membrane material to 260 ℃ after the temperature of the membrane material is reduced to 25 ℃, so as to analyze and obtain the thermal expansion coefficient and the glass transition temperature of the membrane material. Wherein the temperature rising rate is 10 ℃/min.

2. The method for detecting the dielectric constant and the dielectric loss comprises the following steps: a microwave dielectric constant analysis system (brand: AET) is used to measure the film material with a resonant cavity with the frequency of 10GHz, so as to obtain the dielectric constant and dielectric loss value of the film material at the frequency of 10 GHz. Wherein, the dielectric constant measured at the frequency of 10GHz is below 2.9, and the film material is judged to have low dielectric constant; the film material was judged to have a low dielectric loss when the dielectric loss value measured at a frequency of 10GHz was 0.0029 or less.

3. Film roll property: and rolling the film material into a coiled material and observing the film material. When the film material is cracked or the edge of the film material is in a saw-tooth shape, the film material is not good in coiling property. Otherwise, when the film material does not have cracks or the edge presents a saw-tooth shape, the film material has good coiling property.

4. And (5) detecting and analyzing the result.

1. The results of the detection are shown in the following table.

Table 2 results of the tests of examples and comparative examples

TABLE 3 detection results of examples, comparative examples

Table 4 results of the tests of examples, comparative examples

TABLE 5 detection results of examples, comparative examples

2. And (5) analyzing.

As can be seen from Table 2, example 1, comparative example 2 differ in the use of different kinds of initiators. The low dielectric resin composition of example 1 uses an initiator having a benzene ring structure, and therefore the film of example 1 has a dielectric constant of 2.9 or less and a dielectric loss value of 0.0029 or less at a frequency of 10GHz, and the film of example 1 also has good rollability. In contrast to comparative examples 1 and 2, the low dielectric films of comparative examples 1 and 2 have good rollability, but the resin compositions of comparative examples 1 and 2 do not use an initiator having a benzene ring structure, so that the dielectric constant of the film of comparative example 1 is greater than 2.9, the dielectric constant of the film of comparative example 2 is greater than 2.9 and the dielectric loss value is greater than 0.0029, and the resin compositions do not meet the acceptable standards of low dielectric constant and low dielectric loss.

As can be seen from Table 3, examples 1, comparative example 3, comparative example 4 differ in the use of different kinds of crosslinking agents. The low dielectric resin composition of example 1 uses a compound having a styrene structure and no carbonyl group as a crosslinking agent, so the film material of example 1 has a dielectric constant of 2.9 or less and a dielectric loss value of 0.0029 or less at a frequency of 10GHz, and the film material of example 1 also has good rollability. In contrast to comparative examples 3 and 4, the films of comparative examples 3 and 4 have good rollability, but the crosslinking agent of the low dielectric resin composition of comparative examples 3 and 4 includes a compound having carbonyl group, so that the films of comparative examples 3 and 4 have dielectric constants of more than 2.9 and dielectric loss values of more than 0.0029, which do not meet the acceptable standards of low dielectric constants and low dielectric losses.

As can be seen from Table 4, examples 1,2 and comparative examples 5 and 6 differ in the use of soft resins and hard resins of different kinds and contents. The low dielectric resin compositions of examples 1 and 2 use a hard resin comprising a polyphenylene ether having vinyl groups at both ends thereof in an amount of 2300g/mol, and the content of the soft resin is controlled to 50 to 90wt% and the content of the hard resin is controlled to 10 to 50wt% based on 100wt% of the total of the soft resin and the hard resin, so that the films of examples 1 and 2 have a dielectric constant of 2.9 or less and a dielectric loss value of 0.0029 or less at a frequency of 10GHz, and the films of examples 1 and 2 also have good rolling properties. Comparative examples 5 and 6, the electric resin composition of comparative example 5 uses polyphenylene ether having vinyl groups at both ends thereof with a number average molecular weight of 3000g/mol as a hard resin, resulting in a dielectric loss value of the film of comparative example 5 of more than 0.0029, which does not meet the acceptable standards for low dielectric loss. In comparative example 6, however, the content of the soft resin was not controlled to 50 to 90wt% and the content of the hard resin was controlled to 10 to 50wt% based on 100wt% of the total amount of the soft resin and the hard resin, so that the film of comparative example 6 was inferior in the roll property.

As can be seen from Table 5, the main difference between examples 1, 7 and8 is that different kinds of silane compounds were used as the silane coupling agent, wherein the silane compounds used in examples 1, 7 and8 contained 3-methacryloxypropyl trimethoxysilane, vinyl trimethoxysilane and 3- (N-anilino) propyl trimethoxysilane, and further comparing the polarities of the above three silane compounds, the polarities of the above silane compounds were vinyl trimethoxysilane, 3- (N-anilino) propyl trimethoxysilane and 3-methacryloxypropyl trimethoxysilane in this order from the top. The low dielectric resin composition of example 1 uses 3-methacryloxypropyl trimethoxysilane having the lowest polarity as a silane coupling agent, so that the film of example 1 has a dielectric constant of 2.9 or less and a dielectric loss value of 0.0029 or less at a frequency of 10GHz, and the film of example 1 also has good rollability. Comparative examples 7 and8 were observed to have good rollability, but the resin composition of comparative example 7 used vinyltrimethoxysilane having the highest polarity, so that the dielectric constant of the film of comparative example 7 was greater than 2.9 and the dielectric loss value was greater than 0.0029, failing to meet the acceptable standards for low dielectric constant and low dielectric loss; the resin composition of comparative example 8 used vinyltrimethoxysilane and 3- (N-anilino) propyltrimethoxysilane having relatively high polarity as silane coupling agents, so that the film of comparative example 8 had a dielectric constant of greater than 2.9 and a dielectric loss value of greater than 0.0029, and did not meet the acceptable standards for low dielectric constant and low dielectric loss.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (9)

1. A low dielectric resin composition characterized by comprising the following raw materials: initiator, soft resin, hard resin, cross-linking agent, 3- (methacryloxy) propyl trimethoxy silane and inorganic filler;

the mass percentages of the raw materials are as follows:

3wt% or less of initiator 10wt%,5wt% or less of soft resin 20wt%,2wt% or less of hard resin 15wt%,5wt% or less of cross-linking agent 20wt%,0wt% or less of 3- (methacryloyloxy) propyl trimethoxysilane 3wt% or less, and 55wt% or less of inorganic filler 75wt% or less;

The mass of the soft resin accounts for 50-90wt% of the sum of the mass of the soft resin and the mass of the hard resin, and the mass of the hard resin accounts for 10-50wt% of the sum of the mass of the soft resin and the mass of the hard resin;

the initiator has a benzene ring structure; the soft resin is thermoplastic resin, the soft resin comprises hydrocarbon resin and/or polystyrene resin, and the polystyrene resin comprises styrene-butadiene-styrene block copolymer; the hard resin is thermosetting resin, the hard resin comprises polyphenyl ether with vinyl groups at two ends, and the polyphenyl ether with vinyl groups at two ends has a number average molecular weight of 1500g/mol-2500g/mol; the crosslinking agent includes a compound having a styrene structure, and the compound having a styrene structure includes divinylbenzene.

2. The low dielectric resin composition according to claim 1, wherein the mass percentage of the initiator is 4 to 9wt%.

3. The low dielectric resin composition according to claim 1, wherein the mass of the soft resin is 55 to 85wt% of the sum of the mass of the soft resin and the mass of the hard resin.

4. The low dielectric resin composition according to claim 1, wherein the mass of the hard resin is 10 to 40% by weight of the sum of the mass of the soft resin and the mass of the hard resin.

5. The low dielectric resin composition according to claim 1, wherein the crosslinking agent does not include a compound having a hydroxyl group.

6. The low dielectric resin composition according to any one of claims 1 to 5, wherein the initiator comprises dicumyl peroxide; the hard resin also includes polydivinylbenzene and/or divinylbenzene-styrene block copolymers.

7. The low dielectric resin composition according to claim 6, wherein the average particle diameter of the inorganic filler is > 0.4 μm and the maximum particle diameter of the inorganic filler is < 1.0 μm.

8. A low dielectric film prepared by curing the low dielectric resin composition according to any one of claims 1 to 7.

9. Use of the low dielectric resin composition of any one of claims 1-7 or the low dielectric film of claim 8 in wafer packaging and/or build-up.