WO2017107588A1 - Silicone-modified phenol formaldehyde resin, preparation method therefor, and use thereof - Google Patents

Abstract

Provided are a silicone-modified phenol formaldehyde resin, and a resin composition, a resin glue, a cured resin, a prepreg, a laminate, a copper-clad laminate, and a printed circuit board containing the silicone-modified phenol formaldehyde resin. By introducing a C=C double bond and a siloxy group into a side group of phenol formaldehyde resin, the low dielectric property of double bond curing and the desirable heat resistance, weatherability, flame retardancy, dielectric property, and low water absorbency of the siloxy group are combined, so that the phenol formaldehyde resin can provide a high-frequency, high-speed copper-clad laminate with the required properties when the phenol formaldehyde resin is applied.

Description

Silicone modified phenolic resin, preparation method and use thereof Technical field

The invention belongs to the technical field of copper clad laminates, relates to a silicone modified phenolic resin, a preparation method and a use thereof, and further relates to a phenolic resin containing an unsaturated double bond silicone modified, a preparation method thereof, a use thereof, a preparation method thereof and A thermosetting resin composition, a prepreg, a laminate, a copper clad laminate, and a printed circuit board containing the same.

Background technique

With the increase in information traffic in recent years, the demand for high frequency printed circuit boards has become higher and higher. In order to reduce the transmission loss in the high frequency band, electrical insulating materials having excellent electrical characteristics have become the focus of research in the field of copper clad laminates. At the same time, printed substrates or electronic parts using these electrical insulating materials are required to have high heat resistance and high glass transition temperature in order to cope with high-temperature reflow soldering and high-multilayer assembly at the time of mounting.

The phenolic resin has various molecular structures and contains a large amount of benzene ring structure, and has the advantages of high glass transition temperature, good dimensional stability, small linear expansion coefficient, low water absorption, and high heat resistance. However, since the hydroxyl group-curing epoxy generates a secondary hydroxyl group having a strong polar group, the dielectric properties of the phenolic epoxy system are poor, and the requirements of the high-frequency and high-speed fields cannot be met. At present, resins which are cured by double-bond groups are attracting more and more attention in the field, such as vinyl benzyl ether compounds of various structures, vinylbenzyl polyphenylene ether resins, methacrylate-based polyphenylene ether resins. Etc., it relies on the double bond of the terminal group and other resin containing double bond to prepare a laminate by radical reaction or self-curing, and has the characteristics of high glass transition temperature, high heat resistance and high heat and humidity resistance.

Silicone has excellent heat resistance, weather resistance, flame retardancy, dielectric properties and low water absorption. Simultaneous introduction of unsaturated double bonds and siloxy groups in the phenolic resin will further ensure the cured product containing the resin. Heat resistance, dielectric properties and hydrophobicity.

There is a need in the art to develop a phenolic resin having a high glass transition temperature, high heat resistance, high moisture and heat resistance, low water absorption, and good dielectric properties.

Summary of the invention

In view of the problems of the prior art, one of the objects of the present invention is to provide a silicone-modified phenolic resin having the structure of the formula (I):

Wherein Ar is selected from a benzene ring or a naphthalene ring substituted with a C ₁ -C ₈ alkyl group or a C ₁ -C ₈ alkoxy group;

R _{1 is} selected from

R ₃ , R ₄ and R ₅ are each independently selected from a C ₁ -C ₈ substituted or unsubstituted linear or branched alkyl group, a C ₂ -C ₈ substituted or unsubstituted linear or branched alkenyl group, a C ₅ -C ₁₂ substituted or unsubstituted alicyclic group, a C ₆ -C ₂₀ substituted or unsubstituted aryl group or a C ₆ -C ₂₀ substituted or unsubstituted aryloxy group; and R ₃ , R ₄ and R At least one of ₅ is an unsaturated group;

R _{14 is} selected from H, C ₁ -C ₁₄ substituted or unsubstituted linear or branched alkyl, C ₅ -C ₁₂ substituted or unsubstituted alicyclic or C ₁ -C ₁₄ alkoxy.

n is an integer of 1 to 10, for example, 2, 3, 4, 5, 6, 7, 8, and 9.

n is the number of repeating units, and the specific selection can be selected from the demand for improvement in properties such as heat resistance of the resin composition, and those skilled in the art can control by grasping the expertise.

The invention utilizes the reaction of the unsaturated double bond silicone with the hydroxyl group of the phenolic aldehyde, and introduces the C=C double bond and the siloxy group into the side chain of the phenolic resin, and combines the low dielectric and low temperature of the double bond curing. Properties, weather resistance, flame retardancy, dielectric properties and low water absorption, and greater application of phenolic resin in copper clad laminates, providing excellent dielectric properties, heat and humidity resistance, and high temperature and high speed copper clad laminates. Heat.

Preferably, Ar is selected from

Preferably, R ₃ , R ₄ and R ₅ are each independently selected from

And at least one of R ₃ , R ₄ and R ₅ is an unsaturated group.

A second object of the present invention is to provide a process for producing a silicone-modified phenol resin according to one of the objects, wherein R ₃ and R ₄ are each independently selected from a C ₁ - C ₈ substituted or unsubstituted straight A chain or branched alkyl group, a C ₂ -C ₈ substituted or unsubstituted linear or branched alkenyl group, a C ₅ -C ₁₂ substituted or unsubstituted alicyclic group or a C ₆ -C ₂₀ substituted or unsubstituted aromatic And wherein R ₅ is a C ₆ -C ₂₀ substituted or unsubstituted aryloxy group, and wherein at least one of R ₃ , R ₄ and R ₅ is an unsaturated group, the method comprises the steps of:

(1) mixing a dichlorosilane monomer having the formula (II) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a first temperature to carry out the first reaction;

(2) adding a monofunctional phenolic monomer HR ₅ to the reaction system, and heating to a second temperature to continue the second reaction to obtain a silicone-modified phenolic resin having the structure of the formula (I);

Wherein Ar, R ₁ and n have the same meanings as in claim 1 or 2;

Or, when R ₃ , R ₄ and R ₅ are each independently selected from a C ₁ -C ₈ substituted or unsubstituted linear or branched alkyl group, a C ₂ -C ₈ substituted or unsubstituted straight or branched chain An alkenyl group, a C ₅ -C ₁₂ substituted or unsubstituted alicyclic group or a C ₆ -C ₂₀ substituted or unsubstituted aryl group, and when at least one of R ₃ , R ₄ and R ₅ is an unsaturated group, The method includes the following steps:

(a) mixing a monochlorosilane monomer having a structure of the formula (IV) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a third temperature to carry out a third reaction to obtain a structure of the formula (I) Silicone modified phenolic resin;

Wherein Ar, R ₁ and n have the same meanings as in claim 1 or 2;

Further preferably, when R ₃ and R ₄ are each independently selected from

And R ₅ is

The method includes the following steps:

(1) mixing a dichlorosilane monomer having the formula (II) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a first temperature to carry out the first reaction;

(2) adding a monofunctional phenolic monomer HR ₅ to the reaction system, and heating to a second temperature to continue the second reaction to obtain a silicone-modified phenolic resin having the structure of the formula (I);

Wherein Ar, R ₁ , R ₁₄ and n have the same meanings as in claim 1 or 2;

Or, when R ₃ , R ₄ and R ₅ are each independently selected from

The method includes the following steps:

(a) mixing a monochlorosilane monomer having a structure of the formula (IV) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a third temperature to carry out a third reaction to obtain a structure of the formula (I) Silicone modified phenolic resin;

Among them, Ar, R ₁ and n have the same meanings as in claim 1 or 2.

Preferably, the anhydrous solvent is selected from any one or a mixture of any two of tetrahydrofuran, dichloromethane, acetone or methyl ethyl ketone; the mixture is exemplified by a mixture of tetrahydrofuran and dichloromethane, dichloro a mixture of methane and methyl ethyl ketone, a mixture of tetrahydrofuran and methyl ethyl ketone, a mixture of acetone, tetrahydrofuran and methyl ethyl ketone.

Preferably, the first temperature and the second temperature are each independently selected from 0 to 60 ° C, such as 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C 45 ° C, 50 ° C, 55 ° C, 60 ° C, etc.; the first reaction time and the second reaction time are each independently preferably from 2 to 24h, such as 2h, 3h, 5h, 6h, 7h, 9h, 11h, 13h, 15h, 16h, 17h, 19h, 20h, 22h, 24hh, further preferably 3 to 22h, particularly preferably 4 to 20h.

Preferably, the third temperature is selected from 0 to 60 ° C, such as 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, etc.; the third reaction time is preferably from 2 to 24 h, For example, 2h, 3h, 5h, 6h, 7h, 9h, 11h, 13h, 15h, 16h, 17h, 19h, 20h, 22h, 24hh, further preferably 4 to 20h.

A third object of the present invention is to provide a resin composition containing an unsaturated double bond silicone-modified phenol resin as described in one of the objects.

The resin composition may further include other double-bonded resin and initiator other than the silicone-modified phenol resin of the formula (I), and the reaction is a radical reaction. The silicone-modified phenol resin in the resin composition is preferably added in an amount of 10 to 90 parts by weight, and the other resin having a double bond is preferably added in an amount of 10 to 90 parts by weight. The initiator can be added according to actual needs by those skilled in the art.

The "resin having a double bond other than the silicone-modified phenol resin of the formula (I)" according to the present invention is preferably a polyolefin resin or a silicone resin.

The polyolefin resin is preferably any one or a mixture of at least two of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer; the styrene - Butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer can be independently modified by amino group, maleic anhydride, epoxy modified, acrylate modified Sex, hydroxyl modified or carboxyl modified.

Illustratively, the "resin with double bond other than the silicone modified phenolic resin of the formula (I) structure" is selected from the styrene-butadiene copolymer R100 of Sartomer, and the polybutylene of Japan's Soda. Diene B-1000 or Sartomer styrene-butadiene-divinylbenzene copolymer R250.

As a specific embodiment of the present invention, the silicone resin is selected from any one of the following organosilicon compound structures containing an unsaturated double bond:

R ₆ , R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₈ linear alkyl, substituted or unsubstituted C ₁ -C ₈ branched alkyl, substituted or unsubstituted benzene a substituted or unsubstituted C ₂ -C _{10 group} containing C=C; and at least one of R ₆ , R ₇ and R ₈ is substituted or unsubstituted C ₂ -C ₁₀ containing C=C Group; 0 ≤ m ≤ 100;

As another specific embodiment of the present invention, the silicone resin is selected from any one of the following organosilicon compound structures containing an unsaturated double bond:

R _{9 is} selected from a substituted or unsubstituted C ₁ -C ₁₂ linear alkyl group or a substituted or unsubstituted C ₁ -C ₁₂ branched alkyl group; 2 ≤ p ≤ 10, and p is a natural number.

The initiator of the present invention is a free radical initiator, preferably an organic peroxide initiator.

The organic peroxide is exemplarily selected from the group consisting of di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumene peroxy neodecanoate, and t-butyl peroxy neodecanoate. , pivalate peroxypivalate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, peroxidation Tert-butyl acetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane , 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, diter Pentohexoxide, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2, 5-dimethyl-2,5-di-tert-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tetraamyl hydroperoxide, t-butyl hydroperoxide, tert-butyl Base cumene oxide, diisopropylbenzene hydrogen peroxide, peroxycarbonic acid Tert-butyl 2-ethylhexanoate, 2-ethylhexyl peroxybutyl peroxycarbonate, n-butyl 4,4-di(tert-butylperoxy)pentanoate, methyl ethyl ketone peroxide, peroxide ring Any one of hexane or a mixture of at least two.

The resin composition may further comprise a hydrosilycol resin and a hydrosilylation catalyst, the reaction being a hydrosilylation reaction, the amount of the organosilicon modified phenolic resin in the resin composition and the amount of the hydrosilycol resin according to the silicon hydrogen bond and the double The equivalent of the bond is calculated, and the hydrosilylation catalyst can be added according to actual needs by those skilled in the art.

As a specific embodiment of the present invention, the silicon hydride resin of the present invention is selected from any one selected from the group consisting of the following silicon compound structures containing silicon hydrogen bonds:

R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C ₁ -C ₈ branched alkyl, substituted or unsubstituted phenyl or Substituting or H atom; and at least one of R ₁₀ , R ₁₁ and R ₁₂ is H atom; 0 ≤ x ≤ 100;

As another specific embodiment of the present invention, the silicon hydride resin of the present invention is selected from any one selected from the group consisting of the following silicon compound structures containing silicon hydrogen bonds:

R _{13 is} selected from a substituted or unsubstituted C ₁ -C ₁₂ linear alkyl group or a substituted or unsubstituted C ₁ -C ₁₂ branched alkyl group; 2 ≤ y ≤ 10, and y is a natural number.

The hydrosilylation catalyst of the present invention is a platinum catalyst.

Preferably, the resin composition may further include an inorganic filler.

The inorganic filler of the present invention is selected from the group consisting of aluminum hydroxide, boehmite, silica, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomaceous earth, bentonite Or one of the pumice powders or a mixture of at least two.

Preferably, the resin composition may further include a flame retardant.

The flame retardant of the present invention is selected from any one or a combination of at least two of a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. The halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10- Phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, zinc borate, nitrogen-phosphorus expanded, organic polymer flame retardant, phosphorus Any one or a mixture of at least two of a phenol resin or a phosphorus-containing bismaleimide.

The method for producing the resin composition according to the third object of the present invention may be a phenolic resin containing an unsaturated double bond-containing silicone modified by one of the purposes of mixing, stirring, and mixing by a known method, except for one of the purposes. The other silicone-modified phenolic resin is prepared by stirring a resin having another double bond, a silicone hydrogen resin, an initiator, a hydrosilylation catalyst, a filler, and the like.

A fourth object of the present invention is to provide a resin glue obtained by dissolving or dispersing a resin composition according to the third object in a solvent.

Illustratively, the solvent may be exemplified by ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl ethyl ketone. , ketones such as methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; esters such as ethoxyethyl acetate and ethyl acetate; N, N-II A nitrogen-containing solvent such as methylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. The solvent may be used singly or in combination of two or more kinds, and is preferably an aromatic hydrocarbon solvent such as toluene or xylene with acetone, methyl ethyl ketone, methyl ethyl ketone or methyl isobutyl ketone. A ketone flux such as cyclohexanone is used in combination. The amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.

In the process in which the resin composition is dissolved or dispersed in a solvent, an emulsifier may be added for dispersion, and the inorganic filler or the like may be uniformly dispersed in the glue.

A fifth object of the present invention is to provide a cured resin obtained by curing the resin composition as described in the third object.

A sixth object of the present invention is to provide a prepreg comprising a reinforcing material, and a resin composition according to the third object attached thereto by dipping and drying.

Exemplary of the reinforcing material may be carbon fiber, glass fiber cloth, aramid fiber or nonwoven fabric.

The carbon fibers are, for example, T300, T700, T800 of Toray Industries, Japan, and the aramid fibers such as Kevlar fibers, such as 7628 fiberglass cloth and 2116 fiberglass cloth.

A seventh object of the present invention is to provide a copper clad laminate comprising at least one prepreg as described in the sixth object.

An eighth object of the present invention is to provide a laminate comprising at least one prepreg as described in Item 6.

A ninth object of the present invention is to provide a printed circuit board comprising at least one prepreg as described in the sixth object.

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

Introducing C=C double bond and siloxy group into the side base of phenolic resin, combined with low dielectric and silicone heat resistance, weather resistance, flame retardancy, dielectric properties and low water absorption The rate of use of the phenolic resin in the copper clad laminate can provide the excellent dielectric properties, heat and humidity resistance, and heat resistance required for the high-frequency high-speed copper clad laminate.

DRAWINGS

1 is a nuclear magnetic spectrum of the anhydride resin c provided in Preparation Example 3.

detailed description

The technical solution of the present invention will be further described below by way of specific embodiments.

It should be understood by those skilled in the art that the present invention is not to be construed as limited.

Preparation Example 1

27 parts by weight of phenol formaldehyde type phenolic resin and 1000 mL of anhydrous tetrahydrofuran with a stirrer and drops The reaction funnel, the thermometer and the air tube (through nitrogen) were stirred in a reaction vessel until completely dissolved into a uniform solution, and the water vapor in the reactor was removed by continuously flowing nitrogen for 0.5 to 1 hour, and nitrogen gas was kept throughout the reaction. The temperature in the reactor was kept below 20 ° C, and then 48 parts by weight of diallyl dichlorosilane was slowly added dropwise. After the completion of the dropwise addition, the reaction was maintained at 20 ° C for 5 to 10 hours, and then the temperature was raised to 40 to 60 ° C for 10 to 22 hours. Subsequently, 25 parts by weight of phenol was added dropwise to the reaction vessel, and the reaction was carried out at 40 to 60 ° C for 10 to 22 hours. After the completion of the reaction, tetrahydrofuran was removed by distillation under reduced pressure to obtain a linear phenol resin modified with an unsaturated double bond, which was designated as a modified resin a. The functional group equivalent of the resin was 307 g/eq. according to the input ratio, and the conversion of the phenolic hydroxyl group was carried out. The rate is 100%.

Preparation Example 2

43 parts by weight of dicyclopentadiene type phenolic resin and 1000 mL of anhydrous tetrahydrofuran were stirred in a reaction vessel equipped with a stirrer, a dropping funnel, a thermometer and an air tube (through nitrogen) until completely dissolved into a homogeneous solution, and nitrogen gas was continuously passed. The water vapor in the reactor was removed for 0.5 to 1 hour, and nitrogen gas was kept throughout the reaction. At the same time, the temperature in the reactor was kept below 20 ° C, and then 34 parts by weight of methylvinyldichlorosilane was slowly added dropwise. After the completion of the dropwise addition, the reaction was maintained at 20 ° C for 5 to 10 hours, and then the temperature was raised to 40 to 60 ° C for 10 to 22 hours. Subsequently, 25 parts by weight of phenol was added dropwise to the reaction vessel, and the reaction was carried out at 40 to 60 ° C for 10 to 22 hours. After completion of the reaction, tetrahydrofuran was removed by distillation under reduced pressure to obtain a dicyclopentadiene-type phenol resin containing an unsaturated double bond-modified silicone, which was referred to as a modified resin b, and the functional group equivalent of the resin was 347 g/eq. The conversion of the phenolic hydroxyl group was 100%.

Preparation Example 3

50 parts by weight of dicyclopentadiene type phenolic resin and 1000 mL of anhydrous tetrahydrofuran were stirred in a reaction vessel equipped with a stirrer, a dropping funnel, a thermometer and an air tube (through nitrogen) until completely dissolved to a uniform The solution was continuously purged with nitrogen for 0.5 to 1 hour to remove water vapor in the reactor, and nitrogen gas was kept throughout the reaction. At the same time, the temperature in the reactor was kept below 20 ° C, and then 50 parts by weight of methylphenylvinylmonochlorosilane was slowly added dropwise. After the completion of the dropwise addition, the reaction was maintained at 20 ° C for 5 to 10 hours, and then the temperature was raised to 40 to 60 ° C for 10 to 22 hours. After completion of the reaction, tetrahydrofuran was removed by distillation under reduced pressure to obtain a dicyclopentadiene-type phenol resin containing an unsaturated double bond-modified silicone, which was referred to as a modified resin c, and the functional group equivalent of the resin was 331 g/eq. The conversion of the phenolic hydroxyl group was 100%.

Preparation Example 4

64 parts by weight of biphenyl type phenolic resin and 1000 mL of anhydrous tetrahydrofuran were stirred in a reaction vessel equipped with a stirrer, a dropping funnel, a thermometer and an air tube (through nitrogen) until completely dissolved into a homogeneous solution, and nitrogen gas was continuously passed through 0.5~ The water vapor in the reactor was removed for 1 hour, and nitrogen gas was kept throughout the reaction. At the same time, the temperature in the reactor was kept below 20 ° C, and then 36 parts by weight of dimethylvinylmonochlorosilane was slowly added dropwise. After the completion of the dropwise addition, the reaction was maintained at 20 ° C for 5-10 hours, and then the temperature was raised to 40-60 ° C for 10-22 hours. After completion of the reaction, tetrahydrofuran was removed by distillation under reduced pressure to obtain a biphenyl type phenol resin (modified resin d) containing an unsaturated double bond silicone modified, and the functional group equivalent of the resin was 299 g/eq. The conversion rate is 100%.

Figure 1 shows the NMR spectrum of the modified resin d: 1H NMR (DMSO-d6, ppm) NMR spectrum: 0.08 ppm is the chemical shift of two methyl H atoms on Si atoms, and 3.98-4.03 ppm corresponds to The methylene chemical shift in the biphenol aldehyde, 6.75-7.53 ppm corresponds to the chemical shift of the H atom on the phenyl ring in the biphenol aldehyde.

Application Example 1

60 parts by weight of the modified resin a (alkenyl silicone-modified phenol resin) prepared in Example 1, and 40 parts by weight of phenylhydrogen resin SH305 were dissolved in an appropriate amount of methyl ethyl ketone solvent, and adjusted to suit Viscosity. A total of 10 ppm of platinum catalyst was added and stirred well. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the treated glue into the mold and place it at 50 ° C for 1 hour. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5-2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application Example 2

63 parts by weight of the modified resin b (alkenyl silicone-modified phenol resin) prepared in Example 2, and 37 parts by weight of phenylhydrogen resin SH305 were dissolved in an appropriate amount of methyl ethyl ketone solvent, and adjusted to suit Viscosity. A total of 10 ppm of platinum catalyst was added and stirred well. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the processed glue into the mold and leave it at 50 ° C for 1 hour. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5 to 2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application Example 3

62 parts by weight of the modified resin c (alkenyl silicone-modified phenol resin) prepared in Example 3, and 38 parts by weight of phenylhydrogen resin SH305 were dissolved in an appropriate amount of methyl ethyl ketone solvent, and adjusted to be suitable. Viscosity. A total of 10 ppm of platinum catalyst was added and stirred well. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the treated glue into the mold and place it at 50 ° C for 1 hour. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5-2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application Example 4

59 parts by weight of the modified resin d (alkenyl silicone-modified phenol resin) prepared in Example 1, and 41 parts by weight of phenylhydrogen resin SH305 were dissolved in an appropriate amount of methyl ethyl ketone solvent, and adjusted to suit Viscosity. A total of 10 ppm of platinum catalyst was added and stirred well. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the processed glue into the mold and leave it at 50 ° C for 1 hour. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5 to 2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application Example 5

97 parts by weight of the modified resin a (alkenyl silicone-modified phenol resin) prepared in Example 1, and 3 parts by weight of dicumyl peroxide (DCP) were dissolved in an appropriate amount of methyl ethyl ketone solvent, and Adjust to the appropriate viscosity and stir evenly. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the treated glue into the mold and leave it at 120 °C for 2 hours. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5 to 2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application Example 6

97 parts by weight of the alkenyl silicone-modified phenol resin (modified resin c) prepared in Example 3, and 3 parts by weight of dicumyl peroxide (DCP) were dissolved in an appropriate amount of methyl ethyl ketone solvent, and Adjust to the appropriate viscosity and stir evenly. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the treated glue into the mold and leave it at 120 °C for 2 hours. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5 to 2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application comparison 1

70 parts by weight of vinyl phenyl silicone resin, 30 parts by weight of phenylsilicone resin, was added to a total of 10 ppm of a platinum catalyst, and the mixture was stirred uniformly. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the processed glue into the mold and leave it at 50 ° C for 1 hour. After molding, the mold is vacuum laminated and cured in the press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5 to 2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Application comparison 2

97 parts by weight of butylbenzene copolymer Ricon 100, and 3 parts by weight of benzoyl peroxide (BPO) were dissolved in an appropriate amount of methyl ethyl ketone solvent, adjusted to a suitable viscosity, and stirred uniformly. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. Pour the treated glue into the mold and leave it at 90 °C for 2 hours. After molding, the mold is vacuum laminated and cured in a press for 90 min, the curing pressure is 32 kg/cm ² , and the curing temperature is 200 ° C to obtain 0.5-2.0 mm thick. Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

Comparative example 3

97 parts by weight of methacrylate-based polyphenylene ether resin MX9000 and 3 parts by weight of dicumyl peroxide (DCP) were dissolved in an appropriate amount of methyl ethyl ketone solvent, adjusted to a suitable viscosity, and stirred uniformly. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system. The processed gum solution was poured into molds, left for 2 hours at 120 deg.] C, after forming the mold in the vacuum lamination press cured 90min, curable pressure of 32kg / cm ^2, the curing temperature 200 ℃, to give a thickness of 0.5-2.0mm Sheet-like cured product. With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.

The materials used in the embodiments, application examples and application comparative examples of the present invention are as follows:

Phenol formaldehyde linear phenolic resin: 2812, South Korea Momentive.

Dicyclopentadiene type phenolic resin: 9110, Changchun, Taiwan.

Biphenyl type phenolic resin: 7851-H, Japan Minghe.

Methacrylate-based polyphenylene ether resin: MX9000, Sabic.

Styrene-butadiene copolymer: Ricon 100, Satomer.

Dicumyl peroxide: Shanghai Gaoqiao.

Benzoyl peroxide: Guangzhou Chemical Reagent Factory.

Phenylsilicone resin: SH305, Runhe Chemical.

Vinyl phenyl silicone resin: SP606, Runhe Chemical.

Performance Testing:

The test criteria or methods for the parameters involved in Tables 1 and 2 are as follows:

(1) Glass transition temperature (Tg): Measured according to the DMA test method specified in IPC-TM-650 2.4.24.4 using a DMA test.

(2) Dielectric constant and dielectric loss factor: The test was carried out in accordance with the method of IPC-TM-650 2.5.5.9, and the test frequency was 1 GHz.

(3) Thermal decomposition temperature (Td 5%): Measured according to the TGA method specified in IPC-TM-6502.4.24 by thermogravimetric analysis (TGA).

Table 1 Performance test results of the copper clad laminate provided by the application examples

performance

Application example

	1	2	3	4	5	6
Dielectric constant (1GHz)	2.25	2.28	2.25	2.38	2.33	2.29
Dielectric loss (1GHz)	0.0049	0.0041	0.0044	0.0032	0.0042	0.0040
Tg (°C)	188.1	170.5	172.9	164.9	180.6	163.7
Td (5%)	498.7	465.0	474.4	478.6	496.2	470.8

Table 2 Performance test results of copper clad laminates provided by comparative examples

Application Examples 1 to 4 show that the resin composition containing the unsaturated double bond silicone-modified phenol resin synthesized by the present invention has a cured product as compared with a general vinyl phenyl silicone resin (using Comparative Example 1). More excellent dielectric properties, higher glass transition temperature. Examples 5 and 6 show that the self-polymerized cured product of the unsaturated double bond silicone-modified phenolic resin synthesized by the present invention also has superior dielectric properties as compared with the styrene-butadiene copolymer (using Comparative Example 2). , higher glass transition temperature and higher pyrolysis temperature. Compared with the methacrylate-based polyphenylene ether resin (using Comparative Example 3), although the glass transition temperature is slightly lower, the dielectric properties and the thermal decomposition temperature are remarkably improved. Therefore, the organosilicon modified phenolic resin containing an unsaturated double bond is a cross-linking agent with excellent comprehensive performance, and can be used for preparation of a high-frequency circuit substrate, and has great application value.

It should be noted and appreciated that various modifications and improvements can be made to the present invention described in the Detailed Description without departing from the spirit and scope of the invention. Therefore, the scope of the claimed technical solutions is not limited by any particular exemplary teachings presented.

The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (11)

1. A silicone-modified phenolic resin characterized in that the silicone-modified phenolic resin has the structure of the formula (I):

   

   Wherein Ar is selected from a benzene ring or a naphthalene ring substituted with a C ₁ -C ₈ alkyl group or a C ₁ -C ₈ alkoxy group;

   R _{1 is} selected from

   

   

   R ₃ , R ₄ and R ₅ are each independently selected from a C ₁ -C ₈ substituted or unsubstituted linear or branched alkyl group, a C ₂ -C ₈ substituted or unsubstituted linear or branched alkenyl group, a C ₅ -C ₁₂ substituted or unsubstituted alicyclic group, a C ₆ -C ₂₀ substituted or unsubstituted aryl group or a C ₆ -C ₂₀ substituted or unsubstituted aryloxy group, and R ₃ , R ₄ and R At least one of ₅ is an unsaturated group;

   R _{14 is} selected from H, C ₁ -C ₁₄ substituted or unsubstituted straight or branched alkyl, C ₅ -C ₁₂ substituted or unsubstituted alicyclic or C ₁ -C ₁₄ alkoxy;

   n is an integer of 1 to 10.
2. The silicone-modified phenol resin according to claim 1, wherein Ar is selected from the group consisting of

   
3. The silicone-modified phenol resin according to claim 1 or 2, wherein each of R ₃ , R ₄ and R ₅ is independently selected from the group consisting of

   

   -CH ₃ ,

   

   

   And at least one of R ₃ , R ₄ and R ₅ is an unsaturated group.
4. A process for producing a silicone-modified phenol resin according to any one of claims 1 to 3, wherein R ₃ and R ₄ are each independently selected from C ₁ - C ₈ substituted or unsubstituted Linear or branched alkyl, C ₂ -C ₈ substituted or unsubstituted linear or branched alkenyl, C ₅ -C ₁₂ substituted or unsubstituted alicyclic or C ₆ -C ₂₀ substituted or unsubstituted And aryl groups, and wherein R ₅ is a C ₆ -C ₂₀ substituted or unsubstituted aryloxy group, and at least one of R ₃ , R ₄ and R ₅ is an unsaturated group, the method comprises the steps of:

   (1) mixing a dichlorosilane monomer having the formula (II) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a first temperature to carry out the first reaction;

   (2) adding a monofunctional phenolic monomer HR ₅ to the reaction system, and heating to a second temperature to continue the second reaction to obtain a silicone-modified phenolic resin having the structure of the formula (I);

   

   Wherein Ar, R ₁ and n have the same meanings as in claim 1 or 2;

   Or, when R ₃ , R ₄ and R ₅ are each independently selected from a C ₁ -C ₈ substituted or unsubstituted linear or branched alkyl group, a C ₂ -C ₈ substituted or unsubstituted straight or branched chain An alkenyl group, a C ₅ -C ₁₂ substituted or unsubstituted alicyclic group or a C ₆ -C ₂₀ substituted or unsubstituted aryl group, and when at least one of R ₃ , R ₄ and R ₅ is an unsaturated group, The method includes the following steps:

   (a) mixing a monochlorosilane monomer having a structure of the formula (IV) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a third temperature to carry out a third reaction to obtain a structure of the formula (I) Silicone modified phenolic resin;

   

   Wherein Ar, R ₁ and n have the same meanings as in claim 1 or 2;

   Further preferably, when R ₃ and R ₄ are each independently selected from

   

   -CH ₃ ,

   

   

   And R ₅ is

   

   The method includes the following steps:

   (1) mixing a dichlorosilane monomer having the formula (II) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a first temperature to carry out the first reaction;

   (2) adding a monofunctional phenolic monomer HR ₅ to the reaction system, and heating to a second temperature to continue the second reaction to obtain a silicone-modified phenolic resin having the structure of the formula (I);

   Wherein Ar, R ₁ , R ₁₄ and n have the same meanings as in claim 1 or 2;

   Or, when R ₃ , R ₄ and R ₅ are each independently selected from

   

   -CH ₃ ,

   

   

   The method includes the following steps:

   (a) mixing a monochlorosilane monomer having a structure of the formula (IV) with a phenol resin having a structure of the formula (III) in an anhydrous solvent, and raising the temperature to a third temperature to carry out a third reaction to obtain a structure of the formula (I) Silicone modified phenolic resin;

   Wherein Ar, R ₁ and n have the same meanings as in claim 1 or 2;

   Preferably, the anhydrous solvent is selected from any one or a mixture of any two of tetrahydrofuran, dichloromethane, acetone or methyl ethyl ketone;

   Preferably, the first temperature and the second temperature are each independently selected from 0 to 60 ° C; the first reaction time and the second reaction time are each independently preferably from 2 to 24 h, further preferably from 3 to 22 h, particularly preferably. 4 to 20h;

   Preferably, the third temperature is selected from 0 to 60 ° C; and the third reaction time is preferably from 2 to 24 h, further preferably from 3 to 22 h, particularly preferably from 4 to 20 h.
5. A resin composition comprising the unsaturated double bond silicone-modified phenolic resin according to any one of claims 1 to 3;

   Preferably, the resin composition may further include a double bond-containing resin and an initiator other than the silicone-modified phenol resin other than the structure of the formula (I);

   Preferably, the other resin having a double bond is a polyolefin resin or a silicone resin;

   Preferably, the polyolefin resin is preferably any one or a mixture of at least two of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer;

   Preferably, the styrene-butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer may each independently be modified with an amino group, modified with maleic anhydride, epoxy Base modification, acrylate modification, hydroxyl modification or carboxyl modification;

   Preferably, the silicone resin is selected from any one of the following organosilicon compound structures containing an unsaturated double bond:

   

   R ₆ , R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₈ linear alkyl, substituted or unsubstituted C ₁ -C ₈ branched alkyl, substituted or unsubstituted benzene a substituted or unsubstituted C ₂ -C _{10 group} containing C=C; and at least one of R ₆ , R ₇ and R ₈ is substituted or unsubstituted C ₂ -C ₁₀ containing C=C Group; 0 ≤ m ≤ 100,

   or,

   

   R _{9 is} selected from a substituted or unsubstituted C ₁ -C ₁₂ linear alkyl group or a substituted or unsubstituted C ₁ -C ₁₂ branched alkyl group; 2 ≤ p ≤ 10, and p is a natural number;

   Preferably, the resin composition may further include a hydrosilycol resin and a hydrosilylation catalyst;

   Preferably, the silicone resin is selected from any one of the following organosilicon compound structures containing silicon hydrogen bonds:

   

   R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C ₁ -C ₈ branched alkyl, substituted or unsubstituted phenyl or Substituting or H atom; and at least one of R ₁₀ , R ₁₁ and R ₁₂ is H atom; 0 ≤ x ≤ 100,

   or,

   

   R _{13 is} selected from a substituted or unsubstituted C ₁ -C ₁₂ linear alkyl group or a substituted or unsubstituted C ₁ -C ₁₂ branched alkyl group; 2 ≤ y ≤ 10, and y is a natural number;

   Preferably, the resin composition may further be an inorganic filler;

   Preferably, the resin composition may further include a flame retardant.
6. A resin glue obtained by dissolving or dispersing the resin composition according to claim 5 in a solvent.
7. A cured resin of the resin obtained by curing the resin composition according to claim 5.
8. A prepreg characterized in that the prepreg comprises a reinforcing material, and the resin composition according to claim 5 adhered thereto by dipping and drying.
9. A copper clad laminate, characterized in that the copper clad laminate contains at least one prepreg according to claim 8.
10. A laminate characterized in that the laminate contains at least one prepreg according to claim 8.
11. A printed circuit board characterized in that the printed circuit board contains at least one prepreg according to claim 8.

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