Organic titanium chelated silicon-nitrogen resin, resin composition and product thereof

Abstract

The invention discloses organic titanium chelated silicon-nitrogen resin, a resin composition and a product thereof. The structural formula of the organic titanium chelated resin is shown as a formula (I); in the formula (I), R1, R2, R3, R4, R5, R7, R8 and R9 are respectively and independently selected from hydrogen atoms, hydroxyl, amino, C1-C5 alkyl, C1-C5 alkenyl, C6-C12 aryl, C1-C5 alkyl substituted C6-C12 aryl, acrylate, C1-C5 alkyl substituted acrylate, amino, silicon hydrogen or silicon vinyl; and R6 is selected from amino, silicon hydrogen or silicon vinyl. The organic titanium chelated silicon-nitrogen resin provided by the scheme has good dielectric property and relatively good reaction activity, and can obviously improve the crosslinking and curing degree of the resin composition when being applied to the resin composition, so that the peel strength of the circuit substrate can be improved, the thermal expansion coefficient of the circuit substrate is reduced, and the service life of the circuit substrate is prolonged. And meanwhile, the circuit substrate has excellent dielectric property.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, and in particular to an organic titanium chelated silicon nitrogen resin, a resin composition and applications thereof. Background Art

[0002] Polyphenylene ether (PPO / PPE) is widely used in the field of circuit substrates due to its good dielectric properties. However, polyphenylene ether has low polarity and its thermal expansion coefficient is poorly matched with that of copper foil. As a result, the peel strength and thermal expansion coefficient of circuit substrates prepared with polyphenylene ether cannot meet application requirements.

[0003] Although the use of functionalized modified polyphenylene ether, modified hydrocarbon resin and cross-linking agent can improve the peel strength of the circuit substrate, it will lead to a decrease in the dielectric properties of the circuit substrate. The existing technology also adds silicone resin to the resin system to improve the peel strength of the circuit substrate, but the dielectric properties and thermal expansion coefficient still cannot meet the requirements. Summary of the Invention

[0004] Based on this, it is necessary to provide an organic titanium chelated silicon nitrogen resin, a resin composition and its products to address the above problems. The circuit substrate made of the resin composition has excellent dielectric properties, high peel strength and low thermal expansion coefficient.

[0005] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions:

[0006] The first aspect of the present application provides an organic titanium chelate silicon nitrogen resin, the structural formula of the organic titanium chelate silicon nitrogen resin is:

[0007] (1);

[0008] Wherein, R1, R2, R3, R4, R5, R7, R8 and R9 are independently selected from hydrogen atom, hydroxyl group, amino group, C1~C5 alkyl group, C1~C5 alkenyl group, C6~C12 aryl group, C1~C5 alkyl substituted C6~C12 aryl group, acrylate group and C1~C5 alkyl substituted acrylate group, amino group, silicon hydride group or silicon vinyl group; R6 is selected from amino group, silicon hydride group or silicon vinyl group.

[0009] Preferably, the organic titanium chelate silicon nitrogen resin satisfies at least one of the following conditions:

[0010] (1) R7 is selected from a hydrogen atom, a C1-C5 alkenyl group, a C6-C12 aryl group, an amino group, a silyl hydrogen group, or a silyl vinyl group;

[0011] (2) R4 and R8 are independently selected from hydrogen atom, hydroxyl group, amino group, C1-C5 alkyl group, C1-C5 alkenyl group, C6-C12 aryl group, silicon hydride group or silicon vinyl group.

[0012] Preferably, the organic titanium chelate silicon nitrogen resin satisfies at least one of the following conditions:

[0013] (1) In the organic titanium chelate silicon nitrogen resin, the degree of polymerization n is selected from a natural number of 5-13;

[0014] (2) In the organic titanium chelated silicon nitrogen resin, the molar ratio of silicon hydrogen groups to silicon vinyl groups is 1:1 to 1:5.

[0015] The second aspect of the present application provides a resin composition, comprising a modified polyphenylene ether resin, the organic titanium chelated silicon nitrogen resin as described above, a hydrocarbon resin and a cross-linking agent; wherein the modified polyphenylene ether resin is a polyphenylene ether resin whose polyphenylene ether chain end is modified with a group that can participate in a free radical reaction; and the cross-linking agent has a reactive end with at least two reactive groups or can initiate a free radical reaction.

[0016] Preferably, in the resin composition, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the hydrocarbon resin is 40 parts by weight to 80 parts by weight, the amount of the organic titanium chelate silicon nitrogen resin is 4 parts by weight to 20 parts by weight; and the amount of the cross-linking agent is 20 parts by weight to 70 parts by weight.

[0017] Preferably, the modified polyphenylene ether resin satisfies at least one of the following conditions:

[0018] (1) The number average molecular weight of the modified polyphenylene ether resin is 1800-2600;

[0019] (2) The hydroxyl value of the modified polyphenylene ether resin is 1.6-2.6.

[0020] Preferably, the hydrocarbon resin is selected from at least one of polyethylene, polybutadiene, polystyrene, polyisoprene, methylstyrene-ethylene copolymer, methylstyrene-butadiene copolymer, styrene-ethylene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer and styrene-isoprene copolymer.

[0021] Preferably, the cross-linking agent satisfies at least one of the following conditions:

[0022] (1) The purity of the cross-linking agent is ≥95%;

[0023] (2) The crosslinking agent is at least one selected from the group consisting of peroxide crosslinking agents, carboxylic acid and anhydride crosslinking agents, amine crosslinking agents, azo crosslinking agents, and silane crosslinking agents.

[0024] Preferably, the resin composition further comprises at least one of a filler, a catalyst, a coupling agent, a solvent and a flame retardant.

[0025] A third aspect of the present application provides a product made from the resin composition described above, comprising a prepreg, a circuit substrate, and a printed circuit board. The circuit substrate typically comprises an insulating layer and a conductive layer disposed on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or more laminated prepregs described above. The printed circuit board is made from the circuit substrate described above.

[0026] The present invention has the following beneficial effects due to the adoption of the above technical solution:

[0027] 1. The present invention provides an organic titanium chelate silicon nitrogen resin having good dielectric properties and good reactivity. By limiting the side group structure, polymerization degree, and molar ratio of silicon hydride groups to silicon vinyl groups in the organic titanium chelate silicon nitrogen resin, its application in a resin composition can significantly improve the degree of crosslinking and curing of the resin composition;

[0028] 2. The present invention provides a resin composition. By limiting the components in the resin composition, and further limiting the proportion of each component, the organic titanium chelate resin, the modified polyphenylene ether resin, the crosslinking agent and the hydrocarbon resin, a resin composition with excellent dielectric properties is obtained. The resin composition is used in a circuit substrate, can improve the peel strength of the circuit substrate, reduce the thermal expansion coefficient, and at the same time have excellent dielectric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is the structural formula of the organic titanium chelated silicon nitrogen resin in the present invention. DETAILED DESCRIPTION

[0030] The embodiments of the present application are described in detail below. The described embodiments are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0031] In the present invention, except for the components synthesized specifically, all other components and reagents involved are conventional commercial products or can be obtained by conventional techniques in the art. Unless otherwise specified, the materials, methods, and examples of the present invention are illustrative only and not restrictive.

[0032] The present application provides an organic titanium chelated silicon nitrogen resin having good dielectric properties and good reactivity and a preparation method thereof.

[0033] The structural formula of the organic titanium chelate silicon nitrogen resin in this scheme is:

[0034] (1),

[0035] Wherein, R1, R2, R3, R4, R5, R7, R8 and R9 are independently selected from hydrogen atom, hydroxyl group, amino group, C1~C5 alkyl group, C1~C5 alkenyl group, C6~C12 aryl group, C1~C5 alkyl substituted C6~C12 aryl group, acrylate group and C1~C5 alkyl substituted acrylate group, imino group, silicon hydride group or silicon vinyl group; R6 is selected from amino group, silicon hydride group or silicon vinyl group.

[0036] In this solution, the organic titanium chelate silicon nitrogen resin introduces an organic silicon segment to reduce the molecular polarity, so that the synthesized organic titanium chelate silicon nitrogen resin has low dielectric properties while retaining the side group reactivity. When applied to a resin composition, it can significantly improve the cross-linking and curing degree of the resin composition, thereby ensuring that the circuit substrate has excellent dielectric properties and a low thermal expansion coefficient, while improving the bonding force between the resin composition and the surface of the conductive layer, thereby improving the peel strength of the circuit substrate.

[0037] More preferably, in the structural formula (1) of the organic titanium chelated silicon nitrogen resin, R7 is selected from a hydrogen atom, a C1-C5 alkenyl group, a C6-C12 aryl group, an amino group, a silicon hydride group or a silicon vinyl group, which is beneficial to improving the reactivity of the organic titanium chelated silicon nitrogen resin, thereby improving the cross-linking and curing density of the resin composition, and further ensuring that the circuit substrate has excellent dielectric properties while improving the peel strength and reducing the thermal expansion coefficient; R4 and R8 are independently selected from a hydrogen atom, a hydroxyl group, an amino group, a C1-C5 alkyl group, a C1-C5 alkenyl group, a C6-C12 aryl group, a silicon hydride group or a silicon vinyl group, which is beneficial to improving the dielectric properties of the organic titanium chelated silicon nitrogen resin, improving the reactivity, and further improving the peel strength of the circuit substrate, reducing the thermal expansion coefficient, and ensuring that it has excellent dielectric properties.

[0038] Furthermore, n is selected from a natural number of 5-13. The organic titanium chelate resin of this embodiment has multiple cross-linkable sites. Within a suitable molecular weight range, the greater the degree of polymerization of the organic titanium chelate silicon nitrogen resin, the greater the cross-linking density of the product obtained by curing, thereby making the organic titanium chelate resin have excellent dielectric properties.

[0039] If the molecular weight of the organotitanium chelate silane resin is too high (degree of polymerization n>13), it will not dissolve completely in the resin composition system, resulting in a certain amount of resin swelling. This will affect the dielectric properties, peel strength, and thermal expansion coefficient of the circuit substrate after the resin composition is formed. If the molecular weight of the organotitanium chelate silane resin is too low (n<5), the organotitanium chelate silane resin is too active, causing the crosslinker in the resin composition system to preferentially polymerize with the organotitanium chelate silane resin, resulting in poor compatibility between the resins, a lower crosslink density in the resin composition, and poor dielectric properties of the circuit substrate. Within the appropriate molecular weight range, a higher degree of polymerization of the organotitanium chelate silane resin leads to a higher crosslink density in the resin composition, thereby reducing the thermal expansion coefficient of the circuit substrate, optimizing the dielectric properties of the circuit substrate, and improving the peel strength of the circuit substrate.

[0040] The molar ratio of silicon hydride groups to silicon vinyl groups in the organic titanium chelate silicon nitrogen resin is preferably 1:1 to 1:5. Since silicon-hydrogen bonds are very active, adjusting the content of silicon hydride groups in the entire organic titanium chelate silicon nitrogen resin can adjust the reactivity of the resin composition.

[0041] This application also discloses a method for preparing an organic titanium chelated silicon nitrogen resin:

[0042] (1) Blend various monomers selected from methylhydrodichlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane, divinyldichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane in a certain feed ratio, add toluene or n-hexane as a solvent, add diethylamine dropwise, introduce ammonia gas, and terminate the reaction until the pH reaches 9-10. Filter and elute the insoluble solid by-products, remove the solvent, and obtain a silicon nitrogen resin;

[0043] (2) Under anhydrous and oxygen-free conditions, titanium tetrachloride solution is added dropwise to the silicon nitrogen resin until the pH reaches 6-7, the reaction is terminated, and the insoluble solid by-products are filtered and eluted to obtain a titanium-containing silicon nitrogen resin mother liquor;

[0044] (3) The titanium-containing silicon nitrogen resin mother liquor is subjected to thermal polymerization at a reaction temperature of 110-160°C and a reaction time of 3-7 hours; after the reaction is completed, the organic titanium chelated silicon nitrogen resin is obtained by elution and purification.

[0045] The monomers in the above step (1) can be adjusted according to the actual silicon-nitrogen resin to be prepared.

[0046] The present application provides a resin composition comprising a modified polyphenylene ether resin, the organic titanium chelated silicon nitrogen resin as described above, a hydrocarbon resin, and a crosslinking agent; wherein the modified polyphenylene ether resin is a polyphenylene ether resin whose polyphenylene ether chain ends are modified with groups that can participate in free radical reactions; and the crosslinking agent has a reactive end with at least two reactive groups or can initiate a free radical reaction.

[0047] By introducing the organic titanium chelate silicon nitrogen resin into the resin composition, the circuit substrate made of the resin composition has excellent dielectric properties, high peel strength and low thermal expansion coefficient.

[0048] Specifically, the resin composition includes the following components in parts by weight:

[0049] Modified polyphenylene ether resin: 100 parts by weight;

[0050] Hydrocarbon resin: 40-80 parts by weight;

[0051] The above-mentioned organic titanium chelated silicon nitrogen resin: 4-20 parts by weight;

[0052] Cross-linking agent: 20-70 parts by weight.

[0053] In the present application, the groups on the ends of the polyphenylene ether chains of the modified polyphenylene ether resin that can participate in free radical reactions include, but are not limited to, acrylate groups, cyanate groups, epoxy groups, benzyl groups, styryl groups, or allyl groups.

[0054] The number average molecular weight of the modified polyphenylene ether resin is preferably 1800-2600. When the number average molecular weight of the modified polyphenylene ether resin is too low, the crosslinking and curing of the resin composition is insufficient, resulting in a high thermal expansion coefficient of the circuit substrate made from the resin composition. When the number average molecular weight of the modified polyphenylene ether resin is too large, it is easy to agglomerate and separate phases, resulting in deterioration of the dielectric properties of the circuit substrate and a high thermal expansion coefficient. Within the number average molecular weight range of 1800-2600, the higher the number average molecular weight, the more sufficient the crosslinking and curing of the resin composition, and the higher the peel strength of the circuit substrate.

[0055] The hydroxyl value of the modified polyphenylene ether resin is preferably 1.6-2.6. When the hydroxyl value of the modified polyphenylene ether resin is too low, the terminal hydroxyl content is relatively low, which affects the cross-linking and curing degree of the resin composition and causes the thermal expansion coefficient of the circuit substrate to increase. When the hydroxyl value of the modified polyphenylene ether resin is too low, excessive unreacted hydroxyl groups will remain in the resin composition, causing the dielectric properties of the circuit substrate to deteriorate.

[0056] The groups on the ends of the polyphenylene ether chains of the modified polyphenylene ether resin that can participate in free radical reactions are preferably one or more of acrylate groups, cyanate groups, epoxy groups, benzyl groups, styryl groups or allyl groups.

[0057] In some embodiments, the hydrocarbon resin is selected from at least one of polyethylene, polybutadiene, polystyrene, polyisoprene, methylstyrene-ethylene copolymer, methylstyrene-butadiene copolymer, styrene-ethylene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, and styrene-isoprene copolymer.

[0058] In some embodiments, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the hydrocarbon resin is 40 parts by weight to 80 parts by weight, for example, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight.

[0059] In some embodiments, the crosslinking agent may be an inorganic crosslinking agent or a small molecule resin crosslinking agent. Preferably, the crosslinking agent may be selected from at least one of a peroxide crosslinking agent, a carboxylic acid and anhydride crosslinking agent, an amine crosslinking agent, an azo crosslinking agent, and a silane crosslinking agent. Specific examples include but are not limited to triallyl isocyanurate (TAIC), dicumyl peroxide (DCP), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (bis-25), azobisisobutyronitrile (AIBN), and the like.

[0060] In some embodiments, the purity of the cross-linking agent is preferably ≥95%. In this way, the cross-linking agent and the modified polyphenylene ether resin are more compatible in the resin composition system, so that the resin composition has a higher degree of cross-linking and curing, and the obtained circuit substrate has a lower thermal expansion coefficient, higher peel strength, and better dielectric properties.

[0061] In some embodiments, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the crosslinking agent is 20 parts by weight to 70 parts by weight, for example, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight or 70 parts by weight.

[0062] In some embodiments, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the organic titanium chelated silicon nitrogen resin is 4 parts by weight to 20 parts by weight, for example, 4 parts by weight, 8 parts by weight, 12 parts by weight, 16 parts by weight or 20 parts by weight.

[0063] Furthermore, by controlling the amount of each component, the dielectric properties of the circuit substrate can be further improved, the peel strength of the circuit substrate can be increased, and the thermal expansion coefficient of the circuit substrate can be reduced.

[0064] The resin composition may further include at least one of a filler, a catalyst, a coupling agent, a solvent, and a flame retardant.

[0065] The filler includes, but is not limited to, one or more of spherical silica, aluminum oxide, titanium dioxide, and the like. Furthermore, the filler may be surface treated to improve the dielectric properties of the circuit substrate, reduce the coefficient of thermal expansion of the circuit substrate, and increase the peel strength of the circuit substrate. In some embodiments, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the filler is 60 to 160 parts by weight, for example, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, or 160 parts by weight.

[0066] The catalyst can fully crosslink the components in the resin composition, thereby increasing the crosslinking reaction speed of the resin composition. In the present application, the catalyst is a free radical initiator. In some embodiments, the amount of the catalyst is 0.2 parts by weight to 1.0 parts by weight, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, or 1.0 parts by weight, based on 100 parts by weight of the modified polyphenylene ether resin.

[0067] The coupling agent can improve the interfacial bonding of the resin composition. In the present application, the coupling agent is a silane coupling agent. In some embodiments, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the coupling agent is 0.2 parts by weight to 1.0 parts by weight, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, or 1.0 parts by weight.

[0068] The flame retardant may include one or more of a halogen flame retardant, a phosphorus flame retardant, and a nitrogen flame retardant. In some embodiments, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the flame retardant is 30 parts by weight to 50 parts by weight, for example, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or 50 parts by weight.

[0069] The present application also provides a product made from the resin composition as described above, wherein the product includes a prepreg, a circuit substrate, and a printed circuit board.

[0070] The present application does not limit the specific preparation method of the semi-cured sheet using the resin composition. Preferably, the semi-cured sheet is obtained by impregnating or coating the reinforcing material with the resin composition and drying it. The reinforcing material is preferably at least one of glass fiber cloth and quartz fiber cloth.

[0071] The present application also provides a circuit substrate made using the aforementioned prepreg, comprising an insulating layer and a conductive layer disposed on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or more laminated prepregs as described above, and the conductive layer can be copper foil, aluminum foil, nickel foil, silver foil, or alloy foil thereof. This application does not limit this, but copper foil is preferred.

[0072] Specifically, the printed circuit board is made of the circuit substrate described above.

[0073] Specifically, the printed circuit board is mainly made of the circuit substrate through processes such as drilling, hole filling, micro-etching, pre-impregnation, activation, acceleration, chemical copper and copper thickening.

[0074] The effects of the technical solution of the present application are further illustrated below through several specific application examples.

[0075] Example 1:

[0076] A resin composition comprising the following components in parts by weight:

[0077] Modified polyphenylene ether resin (specifically methacrylate-modified polyphenylene ether resin, number average molecular weight 2300, hydroxyl value 2.1): 100 parts by weight;

[0078] Hydrocarbon resin (butadiene-styrene copolymer): 70 parts by weight;

[0079] Organic titanium chelated silicon nitrogen resin (such as structural formula (1), n ​​= 8, silicon hydrogen group / silicon vinyl group = 1:1.3, R1 is vinyl group, R2 is vinyl group, R3 is vinyl group, R4 is methyl group, R5 is silicon vinyl group, R6 is amino group, R7 is methyl group, R8 is silicon vinyl group, and R9 is methyl group): 8 parts by weight;

[0080] Cross-linking agent (specifically triallyl isocyanurate, purity 99.0%): 40 parts by weight;

[0081] Filler (specifically spherical silica filler): 80 parts by weight.

[0082] The above components were mixed in proportion and added with an appropriate amount of toluene solvent. After stirring evenly, the mixture was soaked in glass fiber cloth and baked at 134°C for 2 minutes to obtain a prepreg. 14 prepregs were stacked and covered with copper foil on the upper and lower sides. The copper-clad laminate was obtained after curing under high temperature and high pressure. The curing temperature was 220°C, the curing time was 90 minutes, and the pressure was 25 kg / cm 2 .

[0083] Specifically, the preparation of the above-mentioned organic titanium chelate resin comprises the following steps:

[0084] Methylhydrodichlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane, divinyldichlorosilane, and dimethyldichlorosilane monomers are blended in a molar ratio of 3:2:2:1:2, toluene solvent is added, diethylamine is added dropwise, ammonia gas is introduced until the pH reaches 9-10, the reaction is terminated, insoluble solid by-products are filtered off, and the solvent is removed to obtain a silicon nitrogen resin A;

[0085] 5 parts (by mole) of silane resin A were placed in a reaction kettle. 1 part (by mole) of titanium tetrachloride was slowly added via a constant pressure dripping hole. The pH of the solution was measured every 10 minutes until the solution became acidic and the pH reading on the test paper stabilized at 6. The reaction was then terminated. The reaction solution was allowed to stand for a long time, and the insoluble solid byproducts were removed by filtration to obtain a titanium-containing silane resin mother liquor. The titanium-containing silane resin mother liquor was then subjected to a thermal polymerization reaction (T = 126°C, t = 4 hours) to initially form an organotitanium chelate silane resin. After purification by elution with a toluene / methyl ketone solvent, the organotitanium chelate silane resin having the structure of Example 1 was obtained.

[0086] The synthesized organic titanium chelate silicon nitrogen resin was sent to infrared test: 1170cm -1 The peak at 924 cm is attributed to the absorption peak of -NH2; the asymmetric stretching vibration peak of -Si-N-Si- moves to 924 cm -1 The asymmetric stretching vibration peak of -Si-N-Si- of silicon nitrogen resin A is at 940cm -1 ), at 1030cm -1 A new absorption peak appears at , indicating the existence of Si-N-Ti bonds.

[0087] It should be noted that the preparation methods of different types of organic titanium chelate silicon nitrogen resins in the following other embodiments are similar to the preparation method of the organic titanium chelate resin in Example 1, and can be achieved only by adjusting the types and proportions of raw materials. The infrared test results show that they also have Si-N-Ti bond characteristic peaks and form Si-N-Ti bonds, which will not be described in detail.

[0088] Example 2:

[0089] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0090] In the resin composition of this embodiment, the modified polyphenylene ether resin is a methacrylate-based modified polyphenylene ether resin (number average molecular weight 4000, hydroxyl value 2.1), 100 parts by weight, and the remaining components are the same as those in Example 1.

[0091] Example 3:

[0092] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0093] In the resin composition of this embodiment, the modified polyphenylene ether resin is a methacrylate-based modified polyphenylene ether resin (number average molecular weight 1640, hydroxyl value 2.1), 100 parts by weight, and the remaining components are the same as those in Example 1.

[0094] Example 4:

[0095] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0096] In the resin composition of this embodiment, the modified polyphenylene ether resin is a methacrylate-based modified polyphenylene ether resin (number average molecular weight 2360, hydroxyl value 1.4), 100 parts by weight, and the remaining components are the same as those in Example 1.

[0097] Example 5:

[0098] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0099] In the resin composition of this embodiment, the modified polyphenylene ether resin is a methacrylate-based modified polyphenylene ether resin (number average molecular weight 2320, hydroxyl value 2.8), 100 parts by weight, and the remaining components are the same as those in Example 1.

[0100] Example 6:

[0101] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0102] In the resin composition of this embodiment, the components of the modified polyphenylene ether resin are the same as those in Example 1, the added amount of the modified polyphenylene ether resin is 130 parts by weight, and the other components are the same as those in Example 1.

[0103] Example 7:

[0104] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0105] In the resin composition of this embodiment, the components of the modified polyphenylene ether resin are the same as those in Example 1, the added amount of the modified polyphenylene ether resin is 30 parts by weight, and the other components are the same as those in Example 1.

[0106] Example 8:

[0107] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0108] In the resin composition of this embodiment, the components of the modified polyphenylene ether resin are the same as those in Example 1, the added amount of the modified polyphenylene ether resin is 370 parts by weight, and the other components are the same as those in Example 1.

[0109] Example 9:

[0110] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0111] In the resin composition of this embodiment, the crosslinking agent is triallyl isocyanurate (purity 95.0%), 40 parts by weight, and the remaining components are the same as those in Example 1.

[0112] Example 10:

[0113] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0114] In the resin composition of this embodiment, the composition of the crosslinking agent is the same as that of Example 1, the added amount of the crosslinking agent is 65 parts by weight, and the other components are the same as those of Example 1.

[0115] Example 11:

[0116] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0117] In the resin composition of this embodiment, the component of the crosslinking agent is the same as that in Example 1, the added amount of the crosslinking agent is 15 parts by weight, and the other components are the same as those in Example 1.

[0118] Example 12:

[0119] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0120] In the resin composition of this embodiment, 8 parts by weight of an organic titanium chelated silicon nitrogen resin (such as structural formula (1), n=3, silicon hydrogen group / silicon vinyl group=1:1.3, R1 is vinyl group, R2 is vinyl group, R3 is vinyl group, R4 is methyl group, R5 is silicon vinyl group, R6 is amino group, R7 is methyl group, R8 is silicon vinyl group, and R9 is methyl group) are used. The remaining components are the same as those in Example 1.

[0121] Example 13:

[0122] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0123] In the resin composition of this embodiment, 8 parts by weight of an organic titanium chelated silicon nitrogen resin (such as structural formula (1), n=20, silicon hydrogen group / silicon vinyl group=1:1.3, R1 is vinyl group, R2 is vinyl group, R3 is vinyl group, R4 is methyl group, R5 is silicon vinyl group, R6 is amino group, R7 is methyl group, R8 is silicon vinyl group, and R9 is methyl group) are used. The remaining components are the same as those in Example 1.

[0124] Example 14:

[0125] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0126] In the resin composition of this embodiment, 8 parts by weight of an organic titanium chelated silicon nitrogen resin (such as structural formula (1), n=8, silicon hydrogen group / silicon vinyl group=1:0.5, R1 is H, R2 is vinyl group, R3 is H, R4 is methyl, R5 is silicon vinyl group, R6 is amino group, R7 is methyl, R8 is silicon vinyl group, and R9 is methyl) are used. The remaining components are the same as those in Example 1.

[0127] Example 15:

[0128] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0129] In the resin composition of this embodiment, 8 parts by weight of an organic titanium chelated silicon nitrogen resin (such as structural formula (1), n=8, silicon hydrogen group / silicon vinyl group=1:7, R1 is vinyl group, R2 is vinyl group, R3 is vinyl group, R4 is methyl group, R5 is silicon vinyl group, R6 is silicon vinyl group, R7 is methyl group, R8 is silicon vinyl group, and R9 is vinyl group) are used. The remaining components are the same as those in Example 1.

[0130] Example 16:

[0131] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0132] The resin composition of this embodiment comprises the following components by weight:

[0133] Modified polyphenylene ether resin (specifically methacrylate-modified polyphenylene ether resin, number average molecular weight 2300, hydroxyl value 2.1): 100 parts by weight;

[0134] Hydrocarbon resin (specifically linear styrene-butadiene-styrene block copolymer): 60 parts by weight;

[0135] Organic titanium chelated silicon nitrogen resin (such as structural formula (1), n ​​= 16, silicon hydrogen group / silicon vinyl group = 1:1, R1 is H, R2 is vinyl group, R3 is H, R4 is methyl, R5 is silicon vinyl group, R6 is amino group, R7 is H, R8 is silicon vinyl group, and R9 is methyl): 18 parts by weight;

[0136] Cross-linking agent (specifically trimethylolpropane tris[3-(2-methylaziridinyl)propionate], purity 99.0%): 40 parts by weight;

[0137] Initiator (bis(tert-butylperoxyisopropyl)benzene): 0.8 parts by weight;

[0138] Coupling agent (silane coupling agent): 1 part by weight;

[0139] Flame retardant (phosphate flame retardant): 28 parts by weight.

[0140] Example 17:

[0141] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0142] The resin composition of this embodiment comprises the following components by weight:

[0143] Modified polyphenylene ether resin (specifically methacrylate-modified polyphenylene ether resin, number average molecular weight 2300, hydroxyl value 2.1): 100 parts by weight;

[0144] Hydrocarbon resin (specifically butadiene-styrene copolymer): 70 parts by weight;

[0145] Organic titanium chelated silicon nitrogen resin (such as structural formula (1), n=8, silicon hydrogen group / silicon vinyl group=1:2, R1 is H, R2 is vinyl group, R3 is H, R4 is silicon vinyl group, R5 is silicon vinyl group, R6 is amino group, R7 is silicon hydrogen group, R8 is silicon hydrogen group, and R9 is methyl group): 12 parts by weight;

[0146] Cross-linking agent (specifically triallyl isocyanurate, purity 99.0%): 40 parts by weight;

[0147] Initiator (bis(tert-butylperoxyisopropyl)benzene): 0.8 parts by weight;

[0148] Coupling agent (silane coupling agent): 1 part by weight;

[0149] Flame retardant (phosphate flame retardant): 28 parts by weight;

[0150] Filler (spherical silica filler): 80 parts by weight.

[0151] Example 18:

[0152] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0153] In the resin composition of this embodiment, the components of the organic titanium chelate silicon nitrogen resin are the same as those in Example 1, the added amount of the organic titanium chelate silicon nitrogen resin is 2 parts by weight, and the other components are the same as those in Example 1.

[0154] Example 19:

[0155] The difference between this embodiment and embodiment 1 is that the composition of the resin composition used is different. The preparation method of the prepreg and the copper-clad laminate is the same as that of embodiment 1.

[0156] In the resin composition of this embodiment, the components of the organic titanium chelate silicon nitrogen resin are the same as those in Example 1, the added amount of the organic titanium chelate silicon nitrogen resin is 40 parts by weight, and the other components are the same as those in Example 1.

[0157] Comparative Example 1:

[0158] The difference between this comparative example and Example 1 is that the composition of the resin composition used is different, and the preparation method of the prepreg and the copper-clad laminate is the same as that of Example 1.

[0159] In the resin composition of this comparative example, the polyphenylene ether resin is a benzenesulfonic acid group-modified polyphenylene ether resin (number average molecular weight 2350, hydroxyl value 2.1), 100 parts by weight, and the remaining components are the same as those in Example 1.

[0160] Comparative Example 2:

[0161] The difference between this comparative example and Example 1 is that the composition of the resin composition used is different, and the preparation method of the prepreg and the copper-clad laminate is the same as that of Example 1.

[0162] In the resin composition of this comparative example, the crosslinking agent is a monofunctional phenolic crosslinking agent (purity 99.0%), 40 parts by weight, and the remaining components are the same as those in Example 1.

[0163] Comparative Example 3:

[0164] The difference between this comparative example and Example 1 is that the composition of the resin composition used is different, and the preparation method of the prepreg and the copper-clad laminate is the same as that of Example 1.

[0165] In the resin composition of this comparative example, the organic titanium chelated silicon nitrogen resin is replaced by an organic siloxane resin (molecular weight 2500), 8 parts by weight, and the remaining components are the same as those in Example 1.

[0166] Comparative Example 4:

[0167] The difference between this comparative example and Example 1 is that the composition of the resin composition used is different, and the preparation method of the prepreg and the copper-clad laminate is the same as that of Example 1.

[0168] In the resin composition of this comparative example, no organic titanium chelated silicon nitrogen resin is added, and the remaining components are the same as those in Example 1.

[0169] The copper-clad laminates prepared in Examples 1-19 and Comparative Examples 1-4 were subjected to performance tests using the following methods:

[0170] Dielectric properties Df: Tested in accordance with GB / T43801-2024 Microwave frequency range copper-clad laminate relative dielectric constant and loss tangent test method separated dielectric resonator method @10GHz.

[0171] Peel strength PS: According to the test of "IPC-TM-650 2.4.8.1 Peel Strength and Metal Foil", the peel strength of the copper clad laminate can be obtained, and the unit is N / mm.

[0172] Thermal Expansion Coefficient CTE: According to GB / T2572-2005 Test Method for Average Linear Expansion Coefficient of Fiber Reinforced Plastics, the TMA compression method is used to test the thermal expansion coefficient in the XY plane and the expansion ratio in the Z axis direction.

[0173] The test results are shown in Table 1 below:

[0174] Table 1: Performance test results of the copper-clad laminates prepared in Examples 1-18 and Comparative Examples 1-4

[0175] Group Df (@10GHz) PS (N / mm) X / Y-CTE (ppm) Z-CTE (%) Example 1 0.0008 0.92 9.4 1.53% Example 2 0.0014 0.83 15.4 2.68% Example 3 0.0013 0.85 13.7 2.23% Example 4 0.0012 0.62 14.5 2.27% Example 5 0.0014 0.65 13.4 2.18% Example 6 0.0011 0.80 9.8 1.69% Example 7 0.0015 0.70 12.6 2.11% Example 8 0.0013 0.80 12.2 1.98% Example 9 0.0016 0.70 15.7 2.47% Example 10 0.0013 0.80 10.7 1.77% Example 11 0.0015 0.60 13.9 2.25% Example 12 0.0014 0.86 14.7 2.29% Example 13 0.0012 0.80 11.9 2.02% Example 14 0.0012 0.64 12.7 2.14% Example 15 0.0016 0.70 16.2 2.51% Example 16 0.0026 0.75 17.8 2.68% Example 17 0.0007 0.95 9.2 1.49% Example 18 0.0015 0.60 13.9 2.23% Example 19 0.0013 0.70 11.6 2.07% Comparative Example 1 0.0073 0.20 21.3 3.21% Comparative Example 2 0.0049 0.40 22.9 3.68% Comparative Example 3 0.0065 0.30 23.2 3.56% Comparative Example 4 0.0067 0.10 22.9 3.44%

[0176] It can be seen from Table 1 above that the circuit substrates in the various embodiments of the present application have high peel strength while also having low dielectric properties and low thermal expansion coefficient.

[0177] As can be seen from Example 1 and Comparative Examples 1-4, by introducing an organic titanium chelate silicon nitrogen resin into a modified polyphenylene ether resin, a hydrocarbon resin, and a cross-linking agent, and by limiting the type of the modified polyphenylene ether resin and the type of the cross-linking agent, the copper-clad laminate of the resin composition can have extremely low dielectric properties and a low coefficient of thermal expansion while ensuring peel strength. As can be seen from Examples 1-19, when the addition amount, number-average molecular weight, or hydroxyl value of the modified polyphenylene ether resin, or the purity or addition amount of the cross-linking agent, or the degree of polymerization, side group structure, or silicon hydrogen group to silicon vinyl group ratio of the organic titanium chelate silicon nitrogen resin are not within the preferred range of this solution, although the peeling properties, dielectric properties, and thermal expansion coefficient of the cured product of the resin composition are slightly deteriorated, it can still have high peel strength, low dielectric properties, and a low coefficient of thermal expansion.

[0178] Although the embodiments of the present invention have been shown and described above, it is understandable that the above embodiments are illustrative and cannot be understood as limiting the present invention. Those skilled in the art may change, modify, replace, modify, delete some features, add features, or re-combine features to form a technical solution within the scope of the present invention without departing from the principles and purpose of the present invention. Any simple modifications, equivalent changes, and modifications made to the above embodiments based on the innovative principles of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An organic titanium chelated silicon nitrogen resin, characterized in that The structural formula of the organic titanium chelated silicon nitrogen resin is: （1）； Wherein, R1, R2, R3, R4, R5, R7, R8 and R9 are independently selected from hydrogen atom, hydroxyl group, amino group, C1~C5 alkyl group, C1~C5 alkenyl group, C6~C12 aryl group, C1~C5 alkyl substituted C6~C12 aryl group, acrylate group and C1~C5 alkyl substituted acrylate group, amino group, silicon hydride group or silicon vinyl group; R6 is selected from amino group, silicon hydride group or silicon vinyl group.

2. The organic titanium chelate silicon nitrogen resin according to claim 1, characterized in that The organic titanium chelate silicon nitrogen resin satisfies at least one of the following conditions: (1) R7 is selected from a hydrogen atom, a C1-C5 alkenyl group, a C6-C12 aryl group, an amino group, a silyl hydrogen group, or a silyl vinyl group; (2) R4 and R8 are independently selected from hydrogen atom, hydroxyl group, amino group, C1-C5 alkyl group, C1-C5 alkenyl group, C6-C12 aryl group, silicon hydride group or silicon vinyl group.

3. The organic titanium chelate silicon nitrogen resin according to claim 1, characterized in that The organic titanium chelate silicon nitrogen resin satisfies at least one of the following conditions: (1) In the organic titanium chelate silicon nitrogen resin, the degree of polymerization n is selected from a natural number of 5-13; (2) In the organic titanium chelated silicon nitrogen resin, the molar ratio of silicon hydrogen groups to silicon vinyl groups is 1:1 to 1:

5.

4. A resin composition, characterized in that The invention comprises a modified polyphenylene ether resin, an organic titanium chelated silicon nitrogen resin according to any one of claims 1 to 3, a hydrocarbon resin and a crosslinking agent; wherein the modified polyphenylene ether resin is a polyphenylene ether resin whose polyphenylene ether chain end is modified by a group that can participate in a free radical reaction; and the crosslinking agent has a reactive end with at least two reactive groups or can initiate a free radical reaction.

5. The resin composition according to claim 4, characterized in that In the resin composition, based on 100 parts by weight of the modified polyphenylene ether resin, the amount of the hydrocarbon resin is 40 parts by weight to 80 parts by weight, the amount of the organic titanium chelate silicon nitrogen resin is 4 parts by weight to 20 parts by weight; and the amount of the crosslinking agent is 20 parts by weight to 70 parts by weight.

6. The resin composition according to claim 4, characterized in that The modified polyphenylene ether resin satisfies at least one of the following conditions: (1) The number average molecular weight of the modified polyphenylene ether resin is 1800-2600; (2) The modified polyphenylene ether resin has a hydroxyl value of 1.6-2.6; (3) The group capable of participating in the free radical reaction is selected from at least one of an acrylate group, a cyanate group, an epoxy group, a phenylbenzyl group, a styryl group, and an allyl group.

7. The resin composition according to claim 4, characterized in that The hydrocarbon resin is at least one selected from polyethylene, polybutadiene, polystyrene, polyisoprene, methylstyrene-ethylene copolymer, methylstyrene-butadiene copolymer, styrene-ethylene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer and styrene-isoprene copolymer.

8. The resin composition according to claim 4, characterized in that The cross-linking agent satisfies at least one of the following conditions: (1) The purity of the cross-linking agent is ≥95%; (2) The crosslinking agent is at least one selected from the group consisting of peroxide crosslinking agents, carboxylic acid and anhydride crosslinking agents, amine crosslinking agents, azo crosslinking agents, and silane crosslinking agents.

9. The resin composition according to claim 4, characterized in that The resin composition further comprises at least one of a filler, a catalyst, a coupling agent, a solvent and a flame retardant.

10. A product made from the resin composition according to any one of claims 4 to 9, characterized in that: The products include prepregs, circuit substrates, and printed circuit boards.

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