WO2017088561A1 - Thermosetting resin, thermosetting resin composition comprising same, cured material, prepreg, laminated board, and printed circuit board - Google Patents

Abstract

The present invention provides thermosetting resin having a dihydro-benzoxazine ring structure, a thermosetting resin composition comprising the same, a cured material, prepreg, a laminated board, and a printed circuit board. The thermosetting resin having a dihydro-benzoxazine ring structure is mainly prepared from multifunctional phenol compounds represented by general formula (I) and/or general formula (II) and diamines compounds and aldehyde compounds (c) represented by general formula (a) and/or general formula (b) in a reaction. In the present invention, the thermosetting resin of the dihydro-benzoxazine ring structure is compounded by means of two different multifunctional phenol compounds and diamines compounds, so that the advantages of the two kinds of monomers are effectively combined, the disadvantages of the two kinds of monomers are overcome, and the obtained benzoxazine resin has the excellent comprehensive performance combining low dielectric performance, high heat resistance, high tenacity, low water-absorbing performance, and the like.

Description

Thermosetting resin, thermosetting resin composition containing the same, cured product, prepreg, laminate, and printed circuit board Technical field

The present invention relates to a thermosetting resin, a thermosetting resin composition containing the same, a cured product, a prepreg, a laminate, and a printed circuit board.

Background technique

The rapid development of electronic information technology and consumer electronics has placed new demands on multi-function integrated circuits - reducing their feature size and higher integration. This demand will inevitably impose stricter requirements on electronic packaging materials: For example, a raw material resin having a lower dielectric constant and a low dielectric loss is developed.

Thermosetting resins such as epoxy resin, phenolic resin, bismaleimide resin and unsaturated polyester resin have excellent water resistance, chemical resistance, heat resistance, mechanical strength, etc., and thus come in electronic materials. It has been widely used. However, these thermosetting resins have many disadvantages: for example, the phenolic resin generates volatile by-products in the curing reaction, the flame retardancy of the epoxy resin is poor, and the cost of the bismaleimide resin is high.

Therefore, people are constantly researching and exploring novel structural resins with excellent comprehensive properties. Dihydrobenzoxazine resin (abbreviated as benzoxazine) is a thermosetting resin that has been proven to have a lower dielectric constant. Common benzoxazine has a dielectric constant of about 3.5, and it has good The advantages of heat resistance, flame retardancy and low water absorption make it have a promising application in the field of electronic packaging materials. The general structural formula of the benzoxazine ring is as shown in the formulas (1) and (2), and it has no volatile component generated during ring-opening polymerization and solidification, and therefore has good dimensional stability and excellent mechanical properties.

Although the dielectric properties of the above benzoxazine compounds have been able to meet the more stringent requirements, the higher performance of electronic devices and components in recent years has been stretched. For example, for a resin material of a multilayer substrate constituting an IC package such as a memory or a theoretical processor, a dielectric constant of 100 MHz and 1 GHz at an ambient temperature of 23 ° C is less than 3.5, and under the same conditions. When the dielectric loss factor is less than 0.015, the existing benzoxazine resin is difficult to satisfy.

CN 102584884A discloses a silicon-containing benzoxazine resin which has a low dielectric constant, high heat resistance and has a good toughness due to the introduction of a large number of flexible units in the molecular chain, but such a content The synthesis method of the silicon benzoxazine resin is complicated and costly, and it is difficult to obtain industrial application.

CN 103059296A A novel benzoxazine is synthesized by introducing a PBO-containing benzoxazole structure as a main group into a benzoxazine structure. Although, the invention claims that the resin has a glass transition temperature of 402 ° C, and has a residual carbon ratio of 62% at 800 ° C, a dielectric constant of 2.1 - 2.3, a dielectric loss value of less than 0.003, and the like. However, the invention does not provide data for the corresponding synthesis steps and examples, and thus it is difficult to judge the application prospect.

JP2005239827 proposes a benzoxazine having excellent heat resistance, high toughness and flexibility. However, since the benzoxazine product has a free OH group, it is not very desirable in terms of hygroscopicity and electrical properties.

Summary of the invention

Based on this, one of the objects of the present invention is to provide a benzoxazine thermosetting resin having excellent heat resistance, dielectric properties, toughness, and low water absorption. Another object of the present invention is to provide a thermosetting resin composition, a cured product, a prepreg, a laminate, and a printed circuit board containing the above thermosetting resin.

In order to achieve the above object, the present invention adopts the following technical solutions:

A thermosetting resin having a dihydrobenzoxazine ring structure mainly composed of a polyfunctional phenolic compound represented by the general formula (I) and/or (II), and the formula (a) and/or (b) The diamine compound and the aldehyde compound (c) are reacted to prepare:

Wherein n ₁ , n ₂ , n ₃ and n ₄ are each independently an integer of 0 to 10, such as 0, ₁ , ₂ , ₃ , ₄ , 5, 6, 7, 8, or 9, which may be the same or different. In the present invention, in consideration of reactivity in the synthesis of the above thermosetting resin, heat resistance, mechanical properties and dielectric properties of the cured body, n ₁ , n ₂ , n ₃ and n ₄ are each independently preferably 0-5. Integer.

As a result of intensive studies, the present inventors have found that the above object can be attained by a method for producing a thermosetting resin using a specific aromatic diamine and a specific phenol compound from the viewpoint of improvement in heat resistance, dielectric properties, toughness, and water absorbability.

The aldehyde compound which is the component (c) used in the present invention is not particularly limited, and is preferably formaldehyde. As the formaldehyde, it can be a paraformaldehyde as a polymer or a formalin in the form of an aqueous solution. Used in the form. When paraformaldehyde is used, the progress of the reaction is more stable. Further, as the other aldehyde compound, acetaldehyde, propionaldehyde or butyraldehyde may be used.

The thermosetting resin is a thermosetting resin having a dihydrobenzoxazine ring structure represented by the following formula (IV).

In the formula, X ₁ and X ₂ may be identical or different, that is, in the above formula (IV), X ₁ and X ₂ are either or both of the following structures:

n ₆ and n ₇ are integers from 0 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, or 9, which may be identical or different;

m is an integer from 2 to 15, such as 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. As a preferred technical solution for preparing a thermosetting resin having a dihydrobenzoxazine ring structure, in addition to the polyfunctional phenolic compound represented by the general formula (I) and/or (II), the general formula (a) and/or In addition to the diamine compound and the aldehyde compound (c) shown, a monofunctional phenol compound represented by the formula (III) may be added, which ensures processability such as solubility.

The above monofunctional phenolic compound is a compound having a large molecular weight of a side chain, and Z in the general formula (III) is a carbon atom. The number is 4 or more, preferably 6 or more, and more preferably an organic group having 8 to 20 (for example, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19) carbon atoms. . When the number of carbon atoms increases, the free volume tends to increase and the dielectric constant decreases.

Preferably, the organic group contains a hetero atom, and the hetero atom is N, O or F.

Preferably, in the monofunctional phenolic compound represented by the formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is any one of the following structures:

Wherein n ₅ is an integer of 0 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, or 9.

Preferably, the substituent Z is bonded to the OH group in the para position from the viewpoint of dielectric properties such as non-volatility, dielectric constant and dielectric loss factor at a high temperature, and is a group represented by the following formula Any of them:

Specific examples of the monofunctional phenol compound include 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenylphenol, 4-phenylphenol, 2-hydroxyphenol, 4-benzylphenol, and 2 -hydroxybenzophenone, 4-hydroxybenzophenone, phenyl 4-hydroxybenzoate, 4-phenoxyphenol, 3-benzyloxyphenol phenol, 4-benzyloxyphenol, 4-(1 Any one or a mixture of at least two of 1,3,3-tetramethylbutyl)phenol, 4-α-cumylphenol, 4-adamantylphenol or 4-triphenylmethylphenol .

Preferably, in the present invention, the above polyfunctional phenol compound, diamine compound, and aldehyde compound may be heated and reacted in a suitable solvent, if necessary, with a monofunctional phenol compound.

The solvent to be used is not particularly limited, and a high degree of polymerization is more easily obtained by a phenol compound or a diamine compound as a raw material and a polymer having a good product. Such a solvent can be exemplified An aromatic solvent such as toluene or xylene; a halogen solvent such as chloroform or dichloromethane; an ether solvent such as THF or dioxane;

The reaction temperature and the reaction time are not particularly limited, and it is usually allowed to react at a temperature of from room temperature to about 120 ° C for about 10 minutes to 24 hours. In the present invention, it is particularly preferred to carry out the reaction at 30 to 110 ° C (for example, 40 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C or 100 ° C) for 20 minutes to 9 hours (for example, 1 hour, 2 hours, 3) The reason for the hour, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours is that the reaction proceeds to a polymer capable of exhibiting the function of the thermosetting resin of the present invention.

From the viewpoint of generating an unexpected large molecular weight resin or a three-dimensionally crosslinked polymer under high temperature and long-term reaction, it is preferable to lower the reaction temperature or shorten the reaction time in terms of amination, and at a low temperature and a short time. In view of the inability to synthesize a resin having a sufficiently large molecular weight suitable for coating under the reaction, it is preferred to increase the reaction time or increase the reaction temperature. In addition, the removal of water generated during the reaction to the outside of the system is also an effective method for promoting the reaction. By adding a large amount of a poor solvent such as methanol to the solution after the reaction, the polymer can be precipitated, separated, and dried to obtain a target polymer.

In the present invention, a monofunctional phenol compound or a polyfunctional phenol compound may be further added.

Here, examples of the monofunctional phenolic compound which can be added include the above-mentioned monofunctional phenol compound, and examples of the polyfunctional phenol compound include the above-mentioned polyfunctional phenol or 4,4'-bisphenol and 2 , 2'-bisphenol, 4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylmethane, 2,2'-- Hydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)ethane, 1,1 - bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyl Phenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4- Hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)anthracene, 2,2-bis(4-hydroxyphenyl) Hexafluoropropane, 1,3-bis(4-hydroxyphenoxy)benzene, 1,4-bis(3-hydroxyphenoxy)benzene or 2,6-(bis(2-hydroxyl) Phenyl phenyl) methyl) phenol or the like.

Incidentally, a monofunctional amine compound, a trifunctional amine compound, or another diamine compound may be further used insofar as the properties of the thermosetting resin of the present invention are not impaired. When a monofunctional amine compound is used, the degree of polymerization can be adjusted, and when a trifunctional amine compound is used, a polymer having a branch can be obtained. Further, physical properties can be adjusted by using other diamine compounds in combination. They can be used together with the diamine compounds represented by the general formulae (a) and (b) in the present invention, but in consideration of the reaction order, they may be added to the reaction system at a later stage to cause a reaction.

The above structure can be identified using IR, NMR, GC-MS, and other methods.

The thermosetting resin of the present invention has particularly excellent heat resistance, good electrical properties, low water absorbability, and greatly improved brittleness.

A thermosetting composition containing at least a thermosetting resin as described above.

The thermosetting composition of the present invention contains at least the aforementioned thermosetting resin. The thermosetting composition of the present invention preferably contains the above-mentioned thermosetting resin as a main component, and contains, for example, the above-mentioned thermosetting resin as a main component, and may contain another thermosetting resin as a subcomponent.

Examples of the other thermosetting resin as an auxiliary component include an epoxy resin, a thermosetting modified polyphenylene ether resin, a thermosetting polyimide resin, a silicone resin, a melamine resin, a urea resin, and an acrylic resin. Any one or a mixture of at least two of a phenol resin, an unsaturated polyester resin, a bismaleimide resin, an alkyd resin, a furan resin, a polyurethane resin, or an aniline resin. In the thermosetting resin, any one or at least one of an epoxy resin, a phenol resin, or a thermosetting polyimide resin is preferable from the viewpoint of further improving the heat resistance of the cured product formed of the composition. a mixture of two.

Further, the thermosetting composition of the present invention preferably has at least one, preferably two, dihydrobenzoxazines in the molecule as a subcomponent in a molecule described in the publicly known document. Intramolecular The compound having at least one dihydrophenazine may be used alone or in combination of two or more.

In addition, the thermosetting composition of the present invention may further contain a flame retardant, a ring-forming agent, an antioxidant (anti-aging agent), a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, and an anti-defense agent as needed. Various additives such as an electrostatic agent, an antifogging agent, a filler, a softener, a plasticizer or a colorant. These additives may be used alone or in combination of two or more.

Further, in the preparation of the thermosetting composition of the present invention, a reactive or non-reactive solvent can also be used. The thermosetting resin or thermosetting resin composition of the present invention can be dissolved in an organic solvent for casting, and the solvent is dried to form a film. The thermosetting resin or thermosetting resin composition of the present invention is preferably a composition having a high solubility in an organic solvent such as toluene. This is because when the film is formed by casting in a solvent, there is an advantage in that the amount of the solvent can be reduced, and when the content of the solvent is small, the energy required for evaporation of the solvent is small, the drying time is short, and there is no rapidity. Auxiliary effect of foaming caused by drying.

A cured product obtained from the thermosetting composition as described above.

The cured product of the present invention is a substance which is cured by applying heat to the thermosetting resin or resin composition having thermosetting properties. As the curing method, any conventionally known curing method can be used. Generally, it can be heated at about 120 to 300 ° C for several hours. However, when the heating temperature is too low and the heating time is insufficient, the curing does not become different depending on the case. Sufficient and insufficient mechanical strength. In addition, when the heating temperature is too high and the heating time is too long, depending on the case, side reactions such as decomposition may occur, and the mechanical strength may be poorly lowered. Therefore, it is preferred to select appropriate conditions corresponding to the characteristics of the thermosetting compound used.

Further, when curing is performed, an appropriate curing accelerator may be added. As the curing accelerator, any curing accelerator which is usually used in the ring-opening polymerization of a dihydrobenzoxazine compound can be used, and examples thereof include polyfunctional phenols such as catechol and bisphenol A, and p-toluenesulfonic acid. , sulfonic acid such as phenolsulfonic acid, carboxylic acid such as benzoic acid, salicylic acid, oxalic acid, adipic acid, drilling (II) acetic acid acylate, aluminum (III) acetylacetonate, cobalt (IV) acetylacetone Metal complex such as calcium oxide, cobalt oxide, magnesium oxide, oxidation Metal oxides such as iron, calcium hydroxide, imidazole and its derivatives, diazabicycloundecene, diamines such as diazabicyclononene, and salts thereof, triphenyl Phosphorus compounds such as phosphine, triphenylphosphine·benzoquinone derivatives, triphenylphosphine·triphenylboron, tetraphenylphosphonium tetraphenylborate, and derivatives thereof. These may be used alone or in combination of two or more.

The amount of the curing accelerator to be added is not particularly limited. When the amount of addition is too large, the dielectric constant or dielectric loss factor of the cured product increases, the dielectric properties deteriorate, and mechanical properties are adversely affected. Therefore, it is generally preferred to The curing accelerator is added in a proportion of 5 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of the thermosetting resin.

As described above, the cured product of the present invention comprising the above-mentioned thermosetting resin or the above-mentioned thermosetting composition has a specific benzoxazine structure in the polymer structure, so that excellent dielectric properties can be achieved.

In addition, the cured product of the present invention is excellent in reliability, flame retardancy, moldability, and the like, and has a high glass transition temperature (Tg) due to the thermosetting property of the thermosetting resin or the thermosetting composition, and therefore can be applied to application. The stress portion or the material of the movable portion, and since no volatile by-products are generated during the polymerization, such volatile by-products do not remain in the cured product, and are also preferable in sanitary management.

A prepreg comprising a reinforcing material and the above resin or resin composition adhered to the reinforcing material by impregnation and drying, which is semi-cured or not cured.

The prepreg of the present invention is obtained by semi-curing or not curing the above thermosetting resin or a thermosetting composition containing the same. Here, "semi-cured" means a state in which the thermosetting resin is stopped in the middle of curing, and further, it can be cured.

A laminate obtained from a thermosetting resin as described above.

A laminate comprising a prepreg as described above and laminated by vacuum heating.

The laminate of the present invention can be suitably used for applications such as printed circuit boards, electronic equipment and materials thereof, multilayer substrates requiring excellent dielectric properties, and copper-clad laminates.

A printed circuit board comprising a laminate as described above.

The printed circuit board referred to in the present invention refers to a substrate having a conductive layer on the surface of the laminate of the present invention and having a terminal for electrical connection such as a flexible substrate, or an IC component, a resistor, a capacitor, and the like. The substrate of the coil, etc.

Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects:

The invention uses two different polyfunctional phenolic compounds and diamine compounds to synthesize a thermosetting resin having a dihydrobenzoxazine ring structure, effectively combines the advantages of the two monomers, and overcomes their respective shortcomings. The benzoxazine resin has excellent comprehensive properties such as low dielectric properties, high heat resistance, high toughness and low water absorption, specifically: Td (5%) is 450 to 472 ° C, and Dk/Df (100 MHz) is 2.82-2.92/0.0028-0.0034, Dk/Df (1 GHz) is 2.80-2.87/0.0039-0.0051.

In addition, the method and the obtained product of the invention avoid the performance deficiencies of the benzoxazine resin synthesized by using one monomer, have a synthetic method and have broad application prospects.

detailed description

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

Example 1

(1) Preparation of benzoxazine resin

A mixture of 26.21 g of a mixture of polyfunctional phenolic compounds represented by the formulae (I) and (II) in a mass ratio of 1/1 in chloroform, and a mass ratio of 1/1 represented by the formulas (a) and (b) A mixture of a diamine compound (30.13 g) and a paraformaldehyde (94% of Wako Pure Chemical Industries, Ltd.), 8.05 g (0.25 mol), was allowed to react under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 50.78 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured its molecular weight to be 20,500.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Example 2

(1) Preparation of benzoxazine resin

A mixture of 21.5 g of a mixture of polyfunctional phenolic compounds represented by the formulae (I) and (II) having a mass ratio of 1/2 in chloroform and a mass ratio of 2/1 represented by the formulas (a) and (b) 66.68 g of a mixture of diamine compounds, 7.36 g (0.22 mol) of paraformaldehyde (94% by Wako Pure Chemical Industries, Ltd.), and reacted under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 91.10 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured its molecular weight to be 16,600.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. Evaluation of 5% weight in air atmosphere using TGA at a heating rate of 10 ° C / min The amount is reduced by temperature (Td5). The results are shown in Table 1.

Example 3

(1) Preparation of benzoxazine resin

16.12 g of a mixture of polyfunctional phenolic compounds represented by the formulae (I) and (II) in a mass ratio of 2/1, and 49.77 g of a diamine compound represented by the formula (a), paraformaldehyde (94% by Wako Pure Chemical Industries, Ltd.) 10.64 g (0.32 mol), which was allowed to react under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 62.32 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. The molecular weight of GPC was 17,800.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Example 4

(1) Preparation of benzoxazine resin

A mixture of a polyfunctional phenol compound represented by the formula (I) and (II) in a mass ratio of 1/3 was added to chloroform in a total of 14.33 g, and the diamine compound represented by the formula (b) was 41.46 g, paraformaldehyde. (94% by Wako Pure Chemical Industries, Ltd.) 9.96 g (0.30 mol), which was allowed to react under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 52.38 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured its molecular weight to be 20,100.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Example 5

(1) Preparation of benzoxazine resin

10.75 g of the polyfunctional phenol compound represented by the formula (I), 31.50 g of the diamine compound represented by the formula (a), and paraformaldehyde (94% by Wako Pure Chemical Industries, Ltd.) 6.65 g (0.2 mol) were added to the chloroform. The reaction was allowed to react for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 41.26 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured its molecular weight to be 18,600.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Example 6

(1) Preparation of benzoxazine resin

18.5 g of a polyfunctional phenol compound represented by the formula (II) was added to chloroform, and represented by the formula (a) 55.40 g of a diamine compound and 13.29 g (0.4 mol) of paraformaldehyde (94% by Wako Pure Chemical Industries, Ltd.) were reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 79.20 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured its molecular weight to be 16,500.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Example 7

(1) Preparation of benzoxazine resin

21.50 g of a polyfunctional phenol compound represented by the formula (I) and a mixture of the diamine compound represented by the formula (a) and (b) in a mass ratio of 2/3, 58.20 g of paraformaldehyde ( Manufactured by Wako Pure Chemical Industries, 94%), 13.29 g (0.4 mol), was allowed to react under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 85.00 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured its molecular weight to be 18,500.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constants at 23 ° C, 100 MHz, and 1 GHz were measured by the plate capacitance method. And dielectric loss factor. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Example 8

(1) Preparation of benzoxazine resin

18.5 g of a polyfunctional phenolic compound represented by the formula (II) and a mixture of the diamine compound represented by the formula (a) and (b) in a mass ratio of 2/3, 58.20 g of paraformaldehyde ( Manufactured by Wako Pure Chemical Industries, 94%), 13.29 g (0.4 mol), was allowed to react under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 82 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. GPC measured a molecular weight of 19,000.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Comparative example 1

(1) Preparation of benzoxazine resin

A mixture of polyfunctional phenolic compounds represented by the formulae (I) and (II) in a mass ratio of 1/1 was added to chloroform in a total of 14.33 g of 2,2-bis[4-(4-aminophenoxy)benzene. 30.16 g of propane (Tokyo Chemicals Co., Ltd.), 9.57 g (0.29 mol) of paraformaldehyde (94% by Wako Pure Chemical Industries, Ltd.), and reacted under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 48.31 g. A benzoxazine compound having the following structure is a thermosetting resin as a main component. GPC measured its molecular weight to be 20,500.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Comparative example 2

(1) Preparation of benzoxazine resin

A mixture of polyfunctional phenolic compounds represented by the formulae (I) and (II) in a mass ratio of 1/1 was added to chloroform in a total of 14.33 g, and diphenylamine M (Mitsui Chemical) 24.81 g, nepicone (Wako Pure Chemicals) Preparation, 94%) 9.57 g (0.29 mol), which was allowed to react under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. The product was then filtered and washed with methanol. The washed product was dried under reduced pressure to obtain 42.96 g of a thermosetting resin having a benzoxazine compound having the following structure as a main component. The molecular weight of GPC was 17,000.

(2) Preparation of cured product

The polymer obtained in the step (1) was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Comparative example 3

The bisphenol F type benzoxazine resin was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Comparative example 4

The bisphenol A type benzoxazine resin was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Comparative example 5

The phenolphthalein type benzoxazine resin was kept at 220 ° C for 3 hours by a hot press method to obtain a sheet-like cured product having a thickness of 0.5 mm. The obtained cured body was brown transparent, uniform, and excellent in flexibility. For the obtained cured product, the dielectric constant and dielectric loss factor at 23 ° C, 100 MHz, and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td5) in the air atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The results are shown in Table 1.

Table 1

Dk/Df (100MHz) Dk/Df (1GHz) Td5% (°C) Example 1 2.90/0.0028 2.84/0.0045 450 Example 2 2.92/0.0029 2.87/0.005 472 Example 3 2.88/0.0031 2.83/0.0039 455 Example 4 2.85/0.003 2.86/0.0048 467 Example 5 2.82/0.0034 2.80/0.0044 466 Example 6 2.87/0.003 2.86/0.0041 452 Example 7 2.89/0.0028 2.87/0.0051 471

Example 8 2.83/0.003 2.80/0.0049 469 Comparative example 1 3.14/0.0053 3.12/0.0065 415 Comparative example 2 3.11/0.0051 3.11/0.007 421 Comparative example 3 3.32/0.0045 3.30/0.007 385 Comparative example 4 3.28/0.006 3.30/0.008 392 Comparative example 5 3.35/0.0065 3.36/0.008 388

As can be seen from the data in Table 1, Examples 1-8 show that the polyfunctional phenols of the present invention from the biphenyl structure (I) and the polycyclopentadiene structure (II) and the biphenyl structure of the diamines (a) and poly The macromolecular benzoxazine resin cured product obtained by reacting the diamine (II) having a cyclopentadiene structure with the participation of an aldehyde has a good dielectric constant, a dielectric loss factor, and excellent heat resistance. The performance of the cured product of the benzoxazine resin obtained by using an amine of a non-biphenyl structure or a polycyclopentadiene structure (Comparative Example 1-2) is somewhat different, and an ordinary benzoxazine resin (Comparative Example 3) -5) Both dielectric properties and heat resistance are poor.

The benzoxazine resin disclosed in the present invention and the resin combination containing the same are not widely used in the fields of laminates, copper clad laminates and printed circuit boards, and have great production value.

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 (10)

A thermosetting resin having a dihydrobenzoxazine ring structure mainly composed of a polyfunctional phenolic compound represented by the general formula (I) and/or (II), and the formula (a) and/or (b) The diamine compound and the aldehyde compound (c) are reacted to prepare:

Wherein n ₁ , n ₂ , n ₃ and n ₄ are each independently an integer of 0 to 10, which may be the same or different. The thermosetting resin according to claim 1, wherein each of n ₁ , n ₂ , n ₃ and n ₄ is independently an integer of 0 to 5. The thermosetting resin according to claim 1 or 2, which is a thermosetting resin having a dihydrobenzoxazine ring structure represented by the following formula (IV):

In the formula, X ₁ and X ₂ may be identical or different, and X ₁ and X ₂ are either or both of the following structures:

n ₆ and n ₇ are integers of 0 to 10, which may be identical or different; m is an integer of 2-15. A method for producing a thermosetting resin having a dihydrobenzoxazine ring structure according to any one of claims 1 to 3, which is characterized by comprising a polyfunctional phenol represented by the formula (I) and/or (II) A compound, a diamine compound represented by the formula (a) and/or (b), and an aldehyde compound (c) are further added with a monofunctional phenol compound represented by the formula (III):

The monofunctional phenolic compound is a compound having a large molecular weight of a side chain, wherein Z is an organic group having 4 or more carbon atoms; Preferably, Z is an organic group having 6 or more carbon atoms, preferably 8 to 20 carbon atoms; Preferably, the organic group contains a hetero atom, and the hetero atom is N, O or F; Preferably, in the monofunctional phenolic compound represented by the formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is any one of the following structures:

Where n ₅ is an integer from 0 to 10; Preferably, the substituent Z is bonded to the OH group in the para position and is any one of the groups represented by the following formula:

A thermosetting composition comprising at least the thermosetting resin according to any one of claims 1 to 3. A cured product obtained by curing the thermosetting composition according to claim 5. A prepreg comprising a reinforcing material and the thermosetting resin composition according to claim 5 adhered to the reinforcing material by impregnation and drying. A laminate obtained from the thermosetting resin according to any one of claims 1 to 3. A laminate obtained from the prepreg according to claim 7. A printed circuit board comprising the laminate of claim 8 or 9.