TWI600674B - Dicyclopentadiene-phenol with 2,6 dimethyl phenol copolymer epoxy preparation and use - Google Patents

Description

Manufacture and application of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin

The present invention relates to a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer epoxy resin, and a process for producing the same, and copolymerizing the dicyclopentadiene-phenol resin with 2,6-dimethylphenol The epoxy resin is substituted into the glass fiber laminate composition composition, and the cured product exhibits good heat resistance, high glass transition temperature Tg, low dielectric constant Dk and low loss factor Df, and is suitable for high-performance printed circuit boards, semiconductor packaging materials, etc. High reliability requires insulation materials for electronic components.

In Taiwan patent TW216439, Dicyclopentadiene-phenol epoxy resin is a special skeleton structure epoxy resin, which contains an alicyclic six-membered ring, a five-membered ring and an aromatic benzene ring. Containing dicyclopentadiene structure and excellent heat resistance, low polarity, low water absorption with hardener hardening products, excellent electrical properties (low dielectric constant Dk, low loss factor Df), and dicyclopentadiene The structure has the function of reducing the internal stress of the cured product, and has excellent mechanical properties. Therefore, the dicyclopentadiene-phenol epoxy resin has been used in the glass fiber laminate and the printed circuit board industry, and the dicyclopentadiene-phenol resin is used. The phenolic OH group is further reacted and synthesized into a high performance resin such as Benzoxazine, active ester or phenenyl structure, which has excellent electrical properties, lower dielectric constant and The loss factor is in line with the high frequency, high speed electronic product trend requirements. However, for a long time, we have studied the electrical properties of dicyclopentadiene-phenol epoxy resin, which has better effect on the reduction of dielectric constant Dk and less on the loss factor Df.

In Taiwan patent TW201038151, 2,6-dimethylphenol and an aldehyde are disclosed, which are reacted under an acidic catalyst to synthesize a difunctional 2,6-dimethylphenol aldehyde resin, which is a difunctional 2,6-dimethyl phenol aldehyde resin and an epoxy resin. Epichlorhydrion (ECH) synthesizes difunctional 2,6-dimethylphenol aldehyde epoxy resin in the presence of sodium hydroxide NaOH. 2,6-dimethyl phenol aldehyde resin has a highly symmetrical chemical structure, low molecular dipole The characteristics of the distance can effectively reduce the dielectric constant (Dk) and the loss factor (Df). 2,6-dimethylphenol is also a synthetic low dielectric constant (Dk) and low loss factor (Df) material - polyphenylene ether Resin (PPE) raw material, polyphenylene ether PPE material has a very low loss factor (Df) characteristics, the smaller the loss factor, the smaller the signal transmission loss, and the bifunctional 2,6-dimethylphenol synthesized in the aforementioned patent TW201038151 Although the aldehyde epoxy resin can effectively reduce the dielectric constant (Dk) and the loss factor (Df), the bifunctional 2,6-dimethyl phenol aldehyde epoxy resin structure has a low bridging density and a glass transition temperature Tg. Lower and less heat resistant.

In order to meet the high-speed transmission of electronic communication products, the high-speed and high-frequency signal of electronic devices is an urgent trend. As a result, electronic components are light, thin, short, and small, providing a low dielectric constant ( Dk), a low loss factor (Df) and a resin requiring extremely high heat resistance and a high glass transition temperature Tg are a desirable issue in the printed circuit board industry.

Therefore, in order to solve the above problems, the present invention provides a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer epoxy resin, which is not only a dicyclopentadiene phenol epoxy resin. Resin and 2,6-dimethyl phenol aldehyde epoxy resin These two resins have excellent electrical properties (low dielectric constant Dk, low loss factor Df) and heat resistance better than the above two resins, due to the combination of dicyclopentane The excellent electrical properties of the two resins of diene phenol epoxy resin and 2,6 dimethyl phenol aldehyde epoxy resin, especially the low loss factor Df property of 2,6 dimethyl phenol aldehyde epoxy resin, the second invention Cyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin have lower electrical properties than dicyclopentadiene-phenol The epoxy resin is more excellent, and the copolymer reacts and combines the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol aldehyde resin to form a dicyclopentane. Epoxy-phenol resin and 2,6-dimethyl phenolic resin copolymer epoxy resin have higher functional group reaction than dicyclopentadiene-phenol epoxy resin and 2,6-dimethyl phenol aldehyde epoxy resin The epoxy group, the hardened bridge has higher density, and the heat resistance and mechanical properties are further improved. The novel epoxy resin is substituted into the glass fiber laminate formula, and the hardened material also has a low dielectric constant (Dk) and a low loss factor (Df). Good mechanical properties, high glass transition temperature Tg, and thermosetting resin with excellent heat resistance. It is suitable for copper foil fiberglass laminates, printed circuit boards, semiconductor packaging materials, and meets the high-speed transmission of electronic communication products. The demand for high-speed, high-frequency signals for electronic devices.

The method for preparing the dicyclopentadiene-phenol resin of the present invention and the 2,6-dimethylphenol copolymer epoxy resin is a dicyclopentadiene having a low dielectric constant (Dk) and a low loss factor (Df). The phenol resin and 2,6-dimethylphenol are condensed with an aldehyde compound in the presence of an acidic catalyst to obtain a higher average functional group number (6-12) of dicyclopentadiene-phenol resin and 2,6-dimethyl group. Phenol copolymer phenolic resin, and the dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin and excess epichlorohydrin under NaOH conditions to synthesize dicyclopentadiene-phenol resin and 2 , 6 dimethyl phenol copolymer epoxy resin, the dicyclopentadiene-phenol resin and 2,6 dimethyl phenol copolymer epoxy resin, and common epoxy resin hardeners such as dicyandiamide Dicy, phenolic resin PN hardener, styrene-maleic anhydride copolymer SMA, Benzoxazine resin, polyphenylene ether resin (PPE), active ester resin obtained from epoxy resin has a low dielectric constant ( Dk), low loss factor (Df) with excellent heat resistance and high Tg.

The invention relates to a novel dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer epoxy resin, and the molecular structure is as follows: Wherein X is an integer from 0 to 5, and Y is an integer from 0 to 5; and R represents: hydrogen, C1 to C10 alkyl, phenyl, hydroxyphenyl, and the like.

The preparation of the novel dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin is carried out in two steps, step one: from (a1) dicyclopentadiene-phenol resin (formula 2 below) (a2) 2,6-dimethylphenol, formed by reacting (a3) an aldehyde compound in the presence of an acidic catalyst to form a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer phenolic resin; With respect to 1 mole of phenolic hydroxyl group (phenolic OH) in (a1) dicyclopentadiene-phenol resin, (a2) 2,6 dimethylphenol is 1 to 2.5 moles, (a3) aldehyde compound It is a ratio of 0.8 to 1.5 moles. Step 2: Preparation of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymerization of dicyclopentadiene-phenol resin with 2,6-dimethylphenol copolymer and excess epichlorohydrin under NaOH conditions Epoxy resin, dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer and epichlorohydrin (ECH) equivalent ratio of 1:1~8, dicyclopentadiene-phenol resin The equivalent ratio of the copolymer of 2,6-dimethylphenol and alkali NaOH is 1:0.95-1.1.

The characteristic effect of the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer epoxy resin of the present invention is that the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol are excellent in electricity. (low dielectric constant Dk, low loss factor Df) resin reactive bonding and epoxidation, not only has excellent low dielectric constant Dk, low water absorption characteristics of dicyclopentadiene phenol epoxy resin, and has 2, 6 dimethyl phenol epoxy resin excellent low dielectric constant Dk, low loss factor Df, so the novel dicyclopentadiene-phenol resin and 2,6 dimethyl phenol copolymer epoxy resin (low dielectric constant Dk, low loss factor Df) is better than dicyclopentadiene phenol epoxy resin. The synthetic preparation method is to carry out dicyclopentadiene-phenol resin and 2,6-dimethylphenol under acidic catalyst and aldehyde compound. The condensation dehydration reaction is carried out to bond the two resins, that is, the aldehyde compound is bridged to combine a plurality of reaction points in the dicyclopentadiene-phenol resin with 2,6-dimethylphenol to form a copolymer (the following reaction formula), The number of phenolic hydroxyl groups (phenolic OH) functional groups on the copolymer structure is equal to the number of phenolic hydroxyl groups (n+2) of the dicyclopentadiene-phenol resin plus 2,6 two bonded to the dicyclopentadiene-phenol resin. The number of methylphenols is x+y+2, whereas x+y=n, ie f=2n+4, the copolymer has a higher functional group than the dicyclopentadiene-phenol resin or 2,6-dimethylphenol aldehyde resin. The phenolic hydroxyl group, the number of functional groups of the phenolic hydroxyl group is proportional to the number of equivalents of the synthetic aldehyde compound, and the larger the equivalent number of the aldehyde compound, the more the bridge is combined, the dicyclopentadiene-phenol resin and the 2,6 The higher the number of phenolic hydroxyl functional groups of the methyl phenol copolymer, the number average molecular weight Mn and the phenolic hydroxyl equivalent of 150 g/eq were analyzed by GPC on a gel chromatograph. The theoretical functional group average was calculated according to the theoretical formula: functional group number = Mn phenolic hydroxyl equivalent. The value is 6-10, and the phenolic hydroxyl group of the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer is epoxidized to form a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer ring. Oxygen resin, with high functional group properties, good heat resistance after hardening, high glass transition temperature Tg, low Dk, Df, high heat resistance, high Tg with good expected effect Dicyclopentadiene - phenol resin and an epoxy resin copolymer of 2,6-dimethylphenol.

The invention further relates to a method for producing a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer epoxy resin, which are divided into two steps, step one: from (a1) dicyclopentadiene-phenol 1 mole of hydroxyl group (phenolic OH) and (a2) 2,6 dimethylphenol 1~2.5 moles in the resin, adding acidic catalyst, and dissolving 0.8~1.5 moles of compound in water, dropping In the above reaction mixture, the reaction temperature is 95-115 ° C, and the reaction time of the aldehyde compound aqueous solution is added dropwise for 1 to 6 hours. The commonly used acidic catalysts are methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid, etc. The amount of the acidic catalyst is 0.5 to 5% relative to the amount of the dicyclopentadiene-phenol resin, and the aldehyde compound is formaldehyde, acetaldehyde, glyoxal, benzaldehyde, etc., and the reaction is neutralized, and the 2, 6 dimethyl is removed. The phenol is washed with water and desolvated to obtain a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer phenol resin. Step 2: preparing the dicyclopentadiene-phenol resin obtained from the first step of the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer phenolic resin by using conventional epoxidation conditions and excess epichlorohydrin and NaOH to prepare dicyclopentadiene-phenol resin. Epoxy resin with 2,6-dimethylphenol copolymer, dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin and epichlorohydrin (ECH) equivalent ratio of 1:1 ~8, the equivalent ratio of dicyclopentadiene-phenol resin to 2,6-dimethylphenol copolymer and alkali NaOH is 1:0.95~1.1, epoxidation pre-, main reaction temperature 50~100 °C, then take off Epichlorohydrin, purification reaction, desalting, neutralization, water washing, solution filtration, and solvent removal give the dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin of the present invention.

The invention further discloses an epoxy resin varnish composition for a glass fiber laminate, comprising: a component (1) a dicyclopentadiene-phenol resin of the invention and a 2,6-dimethylphenol copolymer epoxy resin, used The amount of the resin accounts for 40 to 80% of the total amount of the resin (the total amount of the resin is equal to the sum of the components 1 to 4). Ingredients (2) Polyfunctional or difunctional or modified epoxy resin, used in an amount of 1~25% of the total resin, selected from o-cresol novolac epoxy resin, phenolic epoxy resin, benzaldehyde-phenol Functional epoxy resin, dicyclopentadiene-phenol epoxy resin, bisphenol A novolac epoxy resin, tetraphenol ethane phenolic epoxy resin, tris(hydroxyphenyl)methane phenolic epoxy resin, phosphorus ring Oxygen resin, 2,6-dimethylphenol novolac epoxy resin, brominated epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol A Epoxy resin, epoxide and isocyanate copolymer. Ingredients (3) Hardener, used in an amount of 10~50% of the total resin, selected from phenolic resin, bisphenol A phenolic resin, dicyclopentadiene-phenol resin, benzaldehyde-phenol phenolic resin, melamine-phenol Melamine-phenol novolac, active ester hardener, styrene-maleic anhydride copolymer (SMA), bisphenol A benzoxazine, bisphenol F benzoxazine (BPF) Benzoxazine), Dicyclopentadiene-phenol Benzoxazine, polyphenylene ether (PPE). Or the foregoing hardener is composed of any two or more. Ingredients (4) Flame retardant, which accounts for 5~35% of the total amount of resin, contains reactive flame retardant and added flame retardant, and is selected from phosphorus-containing bisphenol A phenolic hardener (phosphorus content 5~10) %), hexaphenoxycyclotriphosphazene (phosphorus content 13.4%, nitrogen content 8%), tetrabromobisphenol A (bromine content 58.5%). Ingredient (5) filler, used in an amount of 1 to 45% of the total formulation varnish composition (solid state calculation, solid formula varnish composition equals the sum of component 1 to component 5), selected from cerium oxide, aluminum hydroxide. Ingredients (six) hardening accelerator, the use amount is 0.01~0.2% (relative to the epoxy resin + hardening dose, that is, the sum of the ingredients 1 to 3), which is selected from the group consisting of dimethyl methine sitting, diphenyl mering, and second Tetramethyl methine sits, benzyl dimethylamine. Ingredients (7) Solvent, the dosage is adjusted to 50~70% of the solid content of the varnish composition, selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, dimethoxyethanol (MCS), propylene glycol methyl ether (PM), and toluene.

The dicyclopentadiene-phenol resin of the present invention and the 2,6-dimethylphenol copolymer epoxy resin, and the cured product obtained by thermosetting the varnish composition thereof can be used for different applications, including, for example, PCB printed circuit boards. Insulation materials for highly reliable motor/electronic components such as EMC semiconductor packages, and coatings and adhesives that require excellent electrical properties and thermal stability.

Advantageous Effects of Invention According to the present invention, there is provided a method and an application for producing a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer epoxy resin, wherein the cured product obtained by the thermosetting reaction of the varnish composition exhibits excellent heat resistance. , low dielectric constant, low loss factor, high Tg and other performance, in line with the future high-speed, high-frequency development trend of the electronics industry.

The invention will be more clearly understood from the following detailed description.

The most prominent feature of the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer epoxy resin of the present invention is that the dicyclopentadiene phenol epoxy resin and the 2,6 dimethyl group are combined by reactive grafting. Phenolic epoxy resin is two excellent electrical structural resins. As a result, the copolymer epoxy resin of the present invention has better electrical properties (low dielectric constant Dk, low loss factor Df) and heat resistance, and Tg characteristics are superior to the above two resins. The invention is characterized in that a dicyclopentadiene-phenol resin and a 2,6-dimethylphenol aldehyde resin are graft-bonded with an aldehyde compound under an acidic catalyst, and then epoxidized with epichlorohydrin to form an epoxy resin, The reaction grafting bond has more epoxy functional groups and higher hardening bridging density, resulting in electrical properties (low dielectric constant Dk, low loss factor Df) and heat resistance, and Tg characteristics are better than the above two resins.

Specifically, the method for producing the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer epoxy resin of the present invention comprises two steps, step one (dicyclopentadiene-phenol resin and 2,6) Synthesis of dimethylphenol copolymer phenolic resin): 1 molar hydroxyl group (phenolic OH) and (a2) 2,6 dimethylphenol 1~2.5 mol from (a1) dicyclopentadiene-phenol resin Adding a solvent with a medium boiling point and low water content (boiling point >110 ° C), adding an acidic catalyst, heating to 95-115 ° C, and dissolving 0.8-1.5 molar compound in water to form 20-50% hydroformide The aqueous solution (if the aldehyde compound is in a liquid state, no aqueous solution is prepared) is added dropwise to the reaction mixture, and the reaction temperature is 95-115 ° C, and the aqueous solution of the aldehyde compound is added dropwise for 1 to 6 hours. The commonly used acidic catalyst is methylsulfonate. Acid (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid, etc., the amount of acid catalyst is 0.5~5% relative to the amount of dicyclopentadiene-phenol resin. The aldehyde compound is formaldehyde, acetaldehyde or glyoxal. , benzaldehyde, etc., the reaction process needs to remove water, the aldehyde compound can be completely reacted. The purpose of adding the solvent is to azeotrope with water and produce water with water. The aqueous phase was removed, the solvent selection methyl isobutyl ketone (of MIBK), toluene, water containing low boiling point of the solvent. The amount of the solvent is 5 to 20% relative to the amount of the dicyclopentadiene-phenol resin. Additive After completion, the ripening reaction is carried out for 30 minutes to 2 hours. After the reaction, the acid is neutralized with an alkali, and the alkali is not limited to industrially common bases such as sodium hydroxide, potassium hydroxide, amines and the like. Neutralize to PH value 6~7 to remove solvent and 2,6-dimethylphenol at a temperature of 175~185°C. After reaching 175~185°C, slowly reduce the vacuum to avoid boiling, and finally to vacuum. <5torr. The vacuum was maintained at 175 to 185 ° C for 1 hour under conditions of 5 torr. Continue to add solvents such as methyl isobutyl ketone (MIBK), toluene, etc., add water for desalting, water washing, filtration and desolvation steps, after desolvation, then dicyclopentadiene-phenol resin and 2,6 dimethyl Phenolic copolymer phenolic resin.

Step 2 (dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin synthesis): the dicyclopentadiene-phenol resin obtained in the first step is copolymerized with 2,6-dimethylphenol Preparation of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin by using epoxidation conditions and excess epichlorohydrin and sodium hydroxide (NaOH), as in steps (1)~(5) . (1) Pre-reaction: the equivalent ratio of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin to epichlorohydrin (ECH) is 1:1~8, and is added to The dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer phenolic resin are used in a 10-40% cosolvent, and the cosolvent is selected such as propylene glycol monomethyl ether (PM) or an alcohol, and then 49.5% hydroxide is added. The equivalent ratio of sodium NaOH, dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin to alkali NaOH is 1:0.1~0.2, pre-reaction temperature is 50~100°C, pre-reaction time is 2~4 hour. (2) Main reaction: 1 equivalent of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin is added to the reactant at a ratio of 49.5% NaOH 0.77 to 0.97 equivalent, and the reaction temperature is 60-65. °C, vacuum degree 160~190torr, main reaction dropping time is 2~5 hours, the main reaction process is carried out by azeotropy of ECH and water, and is returned to the system through the phase separation barrel lower phase ECH, the upper layer water The layer is discharged. (3) De-epichlorohydrin: The excess epichlorohydrin ECH was removed at a temperature of 160 ° C and a vacuum of < 5 torr. (4) Refining reaction: adding 30~50% solid resin solution by adding solvent, adding 20% sodium hydroxide NaOH for purification reaction, adding 20% sodium hydroxide NaOH=measured hydrolyzable chlorine value ÷35.5×40×refining Coefficient 1.5×resin weight 0.2, refined temperature 70~90 °C, the reaction time is 1~3 hours, the reaction is finished, the water is desalted, the mixture is neutralized, washed with water, and the resin solution is filtered. After desolvation, the dicyclopentadiene-phenol resin and 2,6 dimethyl ester of the invention are obtained. Phenolic copolymer epoxy resin.

The method for producing the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer epoxy resin of the present invention is described in more detail, and the steps 1 to 2 are carried out as described above, and step 1 (a1) dicyclopentane is used. 1 molar hydroxyl group (phenolic OH) and (a2) 2,6 dimethylphenol 1~2.5 moles in the ene-phenol resin, added to the medium boiling point low water content solvent (boiling point >110 ° C), and then added acid The catalyst is heated to 95~115 ° C, and the 0.8-1.5 molar compound is dissolved in water to form a 20-50% aqueous solution of aldehydes (if the aldehyde is liquid, no aqueous solution is needed) and the reaction mixture is added dropwise. In order to achieve high conversion and high reaction rate, the water needs to be removed during the reaction process, and the water is taken out by a medium boiling point low water content solvent, and the lower aqueous layer is separated in a phase separation barrel, and the upper layer solvent is removed. By refluxing into the reaction system, the aqueous solution of the aldehyde compound is added dropwise, so that the aldehyde compound can be more efficiently reacted and the reaction is more complete. There are two possibilities for the reaction in this step. One is that the dicyclopentadiene-phenol resin is not only bonded by the reaction of the aldehyde with the self-dicyclopentadiene-phenol resin but also by the aldehyde and 2,6-dimethylphenol. The reaction phase is joined, and the second is 2,6-dimethylphenol bonded by reaction of the aldehyde with its own 2,6-dimethylphenol. The weight average molecular weight of the obtained product is positively correlated with the amount of the aldehyde compound fed, and the aldehyde compound feed equivalent does not exceed the sum of the dicyclopentadiene-phenol resin and the 2,6 dimethylphenol equivalent, and the aldehyde compound feed equivalent is 0.8 to 1.2. For the better range.

Step 2: synthesizing the dicyclopentadiene-phenol resin obtained in the first step and the 2,6-dimethylphenol copolymer phenolic resin to synthesize dicyclopentadiene-phenol resin and 2,6-dimethylphenol by common epoxidation conditions. The epoxy resin is obtained by epoxidizing a dicyclopentadiene-phenol resin with a 2,6-dimethylphenol copolymer phenolic resin in the presence of an excess amount of epichlorohydrin in the presence of sodium hydroxide.

Preferred embodiments of the invention will be described in detail in accordance with the following examples.

Synthesis Example A: (dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy Resin A synthesis)

Dicyclopentadiene-phenol resin (NPEH-772L, South Asia Plastics, softening point 85 ° C) 170g (1 mole hydroxyl), 2,6 dimethylphenol 170g, solvent methyl isobutyl ketone (MIBK 30g, catalyst medium methanesulfonic acid MSA1.7g mixed to raise the temperature to 107 ° C, then 23% of the 23% formaldehyde solution was added dropwise at 107 ° C for 3.5 hours, continued at 107 ° C ripening reaction 1Hr, after the end of the reaction, add 49.5% NaOH 0.8 g of aqueous solution, neutralized to pH = 6-7, heated to 140 ° C dehydration, heated to 185 ° C, slowly reduced vacuum to 5 torr. The temperature and vacuum were maintained at a set value of 185 ° C × 5 torr for 1 hour. After cooling and vacuuming, add solvent 550 g of methyl isobutyl ketone, stir at 80 ° C for 60 minutes, add 50 g of water, leave the layer at 80 ° C, drain the lower layer of brine, add 50 g of water, and let stand at 80 ° C. Layering, draining the lower aqueous layer, and repeating the water washing step once. After the solution is filtered, it is dehydrated at 120 ° C, and the temperature is raised to 180 ° C. The vacuum is lowered to 5 torr, and the solvent methyl isobutyl ketone (MIBK) is removed to obtain dicyclopentadiene-phenol resin and 2,6 dimethyl. The phenolic copolymer phenolic resin A, yield 99.5%, quality condition: average molecular weight Mw 2500, softening point 126 ° C, phenolic hydroxyl equivalent 150 g / eq.

Dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer resin phenolic resin A 150g, epichlorohydrin 555g, propylene glycol monomethyl ether PM 166g, mixed and dissolved, heated to 60 ° C, added 49.5% hydrogen 12.1g of sodium oxide NaOH was pre-reacted for 3 hours. Then, 66g of 49.5% sodium hydroxide was added dropwise to the mixed solution for main reaction. The main reaction temperature was 62 ° C, the vacuum degree was 180 torr, and the main reaction time was 4 hours. After completion at 150 ° C, 10 torr, maintaining 1 hour for dehydration and de-ECH; adding solvent 207 g of methyl isopropanone at 80 ° C for 30 minutes, adding 196 g of pure water, stirring at 80 ° C for 15 minutes, standing still, separating the lower brine layer The analyzed resin had a hydrolyzable chlorine value of 2500 ppm, and was subjected to a purification reaction at 80 ° C, and 4.75 g of 49.5% sodium hydroxide and 2 g of pure water were added to carry out a reaction for 2 hours. The solvent MIBK 276g was added continuously, and 50g of pure water was added, and the mixture was stirred at 80 ° C for 15 minutes, and the lower aqueous layer was drained. 30 g of pure water was added, 20 g of 10% NaH ₂ PO _{4 was} stirred at 80 ° C for 15 minutes. The phase separation was carried out, and the pH value was 6-7. The lower aqueous layer was drained, 40 g of pure water was added, and the mixture was stirred at 80 ° C for 15 minutes, and the lower aqueous layer was drained, and the temperature was raised to 117 ° C for dehydration for 1 hour. After filtration through the solution, the temperature is raised to 150 ° C, the degree of vacuum is gradually reduced to 5 torr, and the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer ring of the present invention are obtained by maintaining at 150 ° C for 5 hours under 5 torr conditions. Oxygen resin A.

Quality condition: epoxy equivalent 228 g/eq, hydrolyzable chlorine 240 ppm, weight average molecular weight Mw 3500.

Synthesis Example B: (Synthesis of dicyclopentadiene-phenol resin with 2,6-dimethylphenol copolymer epoxy resin B)

Dicyclopentadiene-phenol resin (NPEH-772H, Nanya Plastics Co., Ltd., softening point 110 ° C) 180g (1 mole hydroxyl), 2,6 dimethylphenol 170g, solvent methyl isobutyl ketone (MIBK 30g, catalyst medium methanesulfonic acid MSA1.7g mixed to raise the temperature to 107 ° C, then 23% of the 23% formaldehyde solution was added dropwise at 107 ° C for 3.5 hours, continued at 107 ° C ripening reaction 1Hr, after the end of the reaction, add 49.5% NaOH 0.8 g of aqueous solution, neutralized to pH = 6-7, heated to 140 ° C dehydration, heated to 185 ° C, slowly reduced vacuum to 5 torr. The temperature and vacuum were maintained at a set value of 185 ° C × 5 torr for 1 hour. After cooling and vacuuming, add solvent 550 g of methyl isobutyl ketone, stir at 80 ° C for 60 minutes, add 50 g of water, leave the layer at 80 ° C, drain the lower layer of brine, add 50 g of water, and let stand at 80 ° C. Layering, draining the lower aqueous layer, and repeating the water washing step once. After the solution is filtered, it is dehydrated at 120 ° C, and the temperature is raised to 180 ° C. The vacuum is lowered to 5 torr, and the solvent methyl isobutyl ketone (MIBK) is removed to obtain dicyclopentadiene-phenol resin and 2,6 dimethyl. Phenolic copolymer phenolic resin B, yield 99.5%, quality condition: average molecular weight Mw 2800, softening point 129 ° C, phenolic hydroxyl equivalent 154 g / eq.

Dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer resin B 154g, epichlorohydrin 555g, propylene glycol monomethyl ether PM 166g, mixed and dissolved, heated to 60 ° C, added 49.5% sodium hydroxide Pre-reaction was carried out with 12.1g of NaOH for 3 hours. Then, 66g of 49.5% sodium hydroxide was added dropwise to the mixed solution for main reaction. The main reaction temperature was 62 ° C, the vacuum degree was 180 torr, and the main reaction time was 4 hours. The main reaction ended. 150 ° C, 10 torr, maintained for 1 hour for dehydration and de-ECH; adding solvent 207 g of methyl isopropanone dissolved at 80 ° C for 30 minutes, adding 196 g of pure water, stirring at 80 ° C for 15 minutes, leaving the phase separation, draining the lower brine layer; The hydrolyzable chlorine value of the analysis resin was 2200 ppm, and the purification reaction was carried out at 80 ° C, and 1.70 g of 49.5% sodium hydroxide and 2 g of pure water were added, and the reaction was carried out for 2 hours. The solvent MIBK 276g was added continuously, and 50g of pure water was added, and the mixture was stirred at 80 ° C for 15 minutes, and the lower aqueous layer was drained. 30 g of pure water was added, 20 g of 10% NaH ₂ PO _{4 was} stirred at 80 ° C for 15 minutes. The phase separation was carried out, and the pH value was 6-7. The lower aqueous layer was drained, 40 g of pure water was added, and the mixture was stirred at 80 ° C for 15 minutes, and the lower aqueous layer was drained, and the temperature was raised to 117 ° C for dehydration for 1 hour. After filtration through the solution, the temperature is raised to 150 ° C, the degree of vacuum is gradually reduced to 5 torr, and the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer ring of the present invention are obtained by maintaining at 150 ° C for 5 hours under 5 torr conditions. Oxygen resin B.

Quality condition: epoxy equivalent 232 g/eq, hydrolyzable chlorine 210 ppm, weight average molecular weight Mw 3800.

The physical properties of the coatings of Examples 1~5 are as shown in Table 1.

Examples 1 to 5 using the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer epoxy resin of the present invention applied to a glass fiber laminate, a resin varnish having excellent heat resistance and low dielectric constant (Varnish) Formulation composition, the composition of which is detailed in Table 1, using a solvent such as propylene glycol monomethyl ether (PM) or methyl ethyl ketone or acetone to adjust the resin composition of 65% of the resin varnish (Varnish) composition, prepared by conventional methods The fiber laminate is impregnated with the 7628 glass fiber cloth, and then dried at 170 ° C (the temperature of the impregnation machine) for several minutes. By adjusting the drying time, the minimum melt viscosity of the prepreg after drying can be adjusted to be between 4000 and 10000 poise. Finally, 8 prepreg layers are stacked between two pieces of 35-um thick copper foil, and the temperature rising program is controlled under a pressure of 25 kg/cm ² : After hot pressing, a 1.6 mm thick copper foil substrate was obtained.

Comparative example 1~3

Without using the dicyclopentadiene-phenol resin of the present invention and the 2,6-dimethylphenol copolymer epoxy resin, other low dielectric epoxy resins are used as comparative examples, and the formulation composition thereof is shown in Table 2, Comparative Example 1 In order to use benzaldehyde-phenol epoxy resin (Nanya Plastics Co., Ltd. model NPPN-433), Comparative Example 2 used 2,6-dimethylphenol novolac epoxy resin (Nanya Plastics Co., Ltd. model NPPN-260), comparative example 3 is the use of dicyclopentadiene-phenol epoxy resin (Nanya Plastics Co., Ltd. model NPPN-272H).

From the above test results, it is known that the dielectric constant Dk and the damage factor Df of the glass fiber laminate prepared by substituting the dicyclopentadiene-phenol resin of the present invention and the 2,6-dimethylphenol copolymer epoxy resin into the formulation are compared. The benzaldehyde-phenol epoxy resin of Example 1 was lower than the 2,6-dimethylphenol of Comparative Example 2, the dicyclopentadiene-phenol epoxy resin of Comparative Example 3, and the dicyclopentadiene-phenol of the present invention. The resin and the 2,6-dimethylphenol copolymer epoxy resin were substituted into the formulation Tg higher than the comparative examples 1-3.

1. Water absorption test (PCT pressure cooker 2 hours)

The water absorption rate test method is to cut the substrate after etching into a 5 cm ² square test piece, and after drying in an oven at 105 ° C for 2 hr, the test piece is placed in a pressure cooker, the pressure cooker condition is 2 atm × 120 ° C, and after passing through the pressure cooker for 120 min, the recording test is performed. The difference in weight before and after the pressure cooker is the water absorption rate at the initial weight of the test piece.

2.288°C solder heat resistance (2 hours via PCT pressure cooker)

The test method is to immerse the above-mentioned pressure cooker test piece in a 288 ° C soldering furnace to record the time required for the test piece to blast.

3.T-288 heat resistance (including copper)

Analysis by thermomechanical analyzer, the test method is to cut the copper-containing copper foil substrate into 6.35mm ² square test pieces, baked in the oven at 105 ° C × 2 hours, put the test piece on the thermomechanical analyzer test bench, after zeroing The thermomechanical analyzer was heated to 288 ° C at 10 ° C / min and maintained at 288 ° C, and the time required for layering the copper foil substrate of the test piece was recorded.

4. Dielectric constant test:

The test method is to use a 5 cm × 5 cm square test piece of a fiber-optic laminate with a ketone-free laminate, and dry it in an oven at 105 ° C for 2 hr, measure the thickness with a thickness gauge, and then sandwich the test piece into an impedance analyzer (Agilent E4991A). ), the average value of the dielectric constant Dk data of 3 points was measured.

5. Dissipation factor test: The test method is to use a 5 cm × 5 cm square test piece of a fiberglass laminate with ketone foil removed, and baked in an oven at 105 ° C for 2 hr, and the thickness is measured by a thickness gauge, and then the test is performed. The film was clamped into an impedance analyzer (Agilent E4991A), and the Df data of the three points was measured and averaged.

6. Termerature of glass transition test: Differential scanning calorimeter (DSC) was used, and the heating rate was 20 ° C / min.

7. Molecular weight Mw: analyzed by GPC using a gel chromatography and calibrated with a standard molecular weight polystyrene.

Claims (6)

A dicyclopentadiene-phenol resin and a 2,6-dimethylphenol copolymer epoxy resin having the following structure: Wherein x is an integer from 0 to 5, and y is an integer from 0 to 5; and R represents: hydrogen, C1 to C10 alkyl, phenyl, hydroxyphenyl, and the like. The chemical structure of the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer epoxy resin according to claim 1, wherein the manufacturing method comprises the following two steps; Step 1 (dicyclopentadiene) - Synthesis of phenolic resin and 2,6-dimethylphenol copolymer phenolic resin): 1 molar hydroxyl group (phenolic OH) and (a2) 2,6 dimethyl from (a1) dicyclopentadiene-phenol resin 1 to 2.5 moles of phenol, adding medium boiling point low water capacity solvent (boiling point > 110 ° C), then adding acidic catalyst, heating to 95 ~ 115 ° C, and 0.8 ~ 1.5 moles 20 ~ 50% aldehyde compound aqueous solution (If the aldehyde compound is in a liquid state, no aqueous solution is prepared), the reaction mixture is added dropwise to the reaction mixture at a temperature of 95 to 115 ° C, and the aqueous solution of the aldehyde compound is added dropwise for 1 to 6 hours. The acid catalyst is used for methanesulfonic acid. (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid, acid catalyst dosage The amount of the relative dicyclopentadiene-phenol resin is 0.5-5%, the aldehyde compound is formaldehyde, acetaldehyde, glyoxal, benzaldehyde, and the solvent is selected to have a medium boiling point low water content solvent such as methyl isobutyl ketone (MIBK). ), toluene, the amount of solvent is 5~20% relative to the amount of dicyclopentadiene-phenol resin; after the dropwise addition reaction, the ripening reaction is carried out for 30 minutes to 2 hours, and after the reaction, the acid is neutralized with alkali, and the alkali is not Any limitation can be sodium hydroxide, potassium hydroxide, amines; neutralization to pH 6~7, temperature removal solvent and 2,6 dimethylphenol, temperature 175 ~ 185 ° C, temperature 175 ~ 185 ° C After slowly reducing the vacuum so as not to cause a sudden boiling, and finally to a vacuum degree <5torr; vacuum degree <5torr conditions to maintain the temperature of 175 ~ 185 ° C for 1 hour; continue to add solvent is methyl isobutyl ketone (MIBK) or toluene to dissolve The resin is further added with water for desalting, water washing, filtration and desolvation steps, and after desolvation, the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer phenolic resin are obtained; Step 2 (dicyclopentadiene) - Synthesis of phenol resin and 2,6 dimethylphenol copolymer epoxy resin): Dicyclopentadiene-phenol resin obtained in the first step 2,6-Dimethylphenol Copolymer Phenolic Resin Preparation of Dicyclopentadiene-Phenol Resin and 2,6-Dimethylphenol Copolymer Ring by Common Epoxidation Conditions and Excess Ethyl Chloropropane and Sodium Hydroxide (NaOH) Oxygen resin, (1) pre-reaction, the equivalent ratio of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin to epichlorohydrin (ECH) is 1:1~8, and added The relative solvent of the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol copolymer is 10-40%, the co-solvent is selected from the group consisting of propylene glycol monomethyl ether (PM) or alcohol, and then 49.5% sodium hydroxide is added. The equivalent ratio of the dicyclopentadiene-phenol resin to the 2,6-dimethylphenol copolymer phenolic resin and sodium hydroxide (NaOH) is 1:0.05-0.2, the pre-reaction temperature is 50-100 ° C, and the pre-reaction time 2 ~4 hours; (2) The main reaction is added dropwise to the reactant with 1 equivalent of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin in a ratio of 0.77 to 0.92 equivalent of 49.5% sodium hydroxide. The reaction temperature is 60~65°C, the degree of vacuum is 160~190torr, the main reaction time is 2~5 hours; (3) the excess epichlorohydrin is removed by the temperature of 160°C, the vacuum degree is less than 5torr; (4) the solvent is added to prepare 30~ 50% solid resin solution, adding 20% sodium hydroxide for purification reaction, purification temperature 70~90 °C, The reaction time is 1 to 3 hours, and the reaction is completed by adding water and desalting liquid, neutralizing, washing with water, and filtering the resin solution. After desolvation, the dicyclopentadiene-phenol resin as described in claim 1 is obtained. Epoxy resin with 2,6 dimethylphenol copolymer. An epoxy resin varnish composition for a glass fiber laminate, comprising the following components: (1) copolymerization of a dicyclopentadiene-phenol resin and 2,6-dimethylphenol as described in claim 1 Epoxy resin, the proportion of the total amount of resin is 40~80% (the total amount of resin is defined as the sum of component (1) to component (4)); (2) polyfunctional or difunctional or modified epoxy resin, The amount of use is 1~25% of the total resin, which is selected from the group consisting of o-cresol novolac epoxy resin, novolac epoxy resin, benzaldehyde-phenol polyfunctional epoxy resin, dicyclopentadiene-phenol epoxy resin, double Phenolic A type phenolic epoxy resin, tetraphenol ethane phenolic epoxy resin, tris(hydroxyphenyl)methane phenolic epoxy resin, phosphorus-containing epoxy resin, 2,6-dimethylphenol novolac epoxy resin, bromination Epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol A epoxy resin, epoxy resin and isocyanate copolymer; (3) hardener, the amount of use is 10~50% of the total resin, selected from Phenolic resin, bisphenol A phenolic resin, dicyclopentadiene-phenol resin, benzaldehyde-phenol phenolic resin, melamine-phenol novol Ac), active ester hardener, styrene-maleic anhydride copolymer (SMA), bisphenol A benzoxazine, BPF Benzoxazine, dicyclopentan Dicyclopentadiene-phenol Benzoxazine, polyphenylene ether (PPE); or two or more of the foregoing hardeners; (iv) Flame retardant, the amount of resin used in the total 5~ 35%, including reactive flame retardant and additive flame retardant, selected from phosphorus-containing bisphenol A phenolic hardener (phosphorus content 5~10%), phosphorus-containing bisphenol F phenolic hardener, hexaphenoxy Cyclotriphosphazene (phosphorus content 13.4%, nitrogen content 8%), tetrabromobisphenol A (bromine content 58.5%); (5) Filling agent, the amount of use is 1~45% of the total formula varnish composition (solid state calculation, the formula varnish composition (solid state) is equal to the sum of component 1 to component 5), is selected from cerium oxide, aluminum hydroxide; Hardening accelerator, the amount used is 0.01~0.2% (relative to the epoxy resin + hardening dose, that is, the sum of the ingredients 1 to 3); it is selected from the group consisting of dimethyl methoxide, diphenyl mercapine, and diethyl tetramethyl Keimi sit, benzyl dimethylamine; (7) solvent, the amount is adjusted to adjust the composition of the varnish composition 50~70%, selected from acetone, butanone, cyclohexanone, dimethoxyethanol (MCS), Propylene glycol methyl ether (PM), toluene, dimethylformamide. The composition (2) phosphorus-containing epoxy resin in the composition of claim 3, which is 10-(2',5'-dihydroxyphenyl)-9,10-dihydro-9-ox-10-phosphorus An addition product of phenanthrene-10-oxide and o-cresol novolac epoxy resin or phenolic epoxy resin. The composition (ii) an epoxy resin and an isocyanate copolymer in the composition of claim 3, wherein the isocyanate is diphenylmethane diisocyanate (MDI), toluene isocyanate (TDI) or the isomers. The composition of the composition of claim 3, (4) phosphorus-containing bisphenol A type hardener and phosphorus-containing bisphenol F type hardener, 10-(2',5'-dihydroxyphenyl)-9 , 10-dihydro-9-oxo-10 phenanthrene-10-oxide and bisphenol A formaldehyde resol phenolic resin compound or bisphenol F formaldehyde resol phenolic resin compound reaction adduct (phosphorus content 5~10%) .