CN115362194A - Polyfunctional vinyl resin and method for producing same - Google Patents
Polyfunctional vinyl resin and method for producing same Download PDFInfo
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- CN115362194A CN115362194A CN202180025507.0A CN202180025507A CN115362194A CN 115362194 A CN115362194 A CN 115362194A CN 202180025507 A CN202180025507 A CN 202180025507A CN 115362194 A CN115362194 A CN 115362194A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/10—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer reinforced with filaments
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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Abstract
The invention provides a resin material which has a low dielectric constant, a low dielectric loss tangent, a high thermal conductivity and a high heat resistance. Provided are a polyfunctional vinyl resin and a resin composition obtained by aromatic vinylation of phenolic hydroxyl group of a phenol aralkyl resin having a biphenyl structure in the skeleton and having two or more phenolic hydroxyl groups. The multifunctional vinyl resin has good dielectric properties and high thermal conductivity, and is suitable for electronic materials and composite materials.
Description
Technical Field
The present invention relates to a multifunctional vinyl resin and a multifunctional vinyl resin composition having both low dielectric loss tangent and high thermal conductivity, which are useful for printed boards, sealing materials, casting materials, and the like of electronic devices, and a cured product thereof.
Background
As communication speeds and communication traffic increase, high-speed communication techniques have been actively studied for increasing signal transmission speeds, for example, for printed boards, packaging materials, and casting materials used in communication devices. Electronic materials for such applications are required to have a reduced dielectric loss, and curable resins capable of forming a multilayer structure are also required for printed circuit board applications.
On the other hand, since such electronic operation components that process data having a large amount of information generate a large amount of heat, and a problem such as a decrease in processing speed of the electronic operation components due to heat accumulation occurs, various methods such as a method of mounting a heat conductive member such as a copper coin or a copper inlay on a printed circuit board as a technique for appropriately cooling the printed circuit board by a heat sink or the like (patent document 1) and a method of specifying the shape of a filler to be blended (patent document 2) are known. However, such a method is not preferable because it increases the weight and increases the size of the apparatus.
Further, as a method for improving the thermal conductivity in the sealing material composition, a method of removing heat from the electronic operation member by examining the kind and amount of various fillers is adopted, and the thermal conductivity is improved by increasing the amount of the fillers, but the viscosity of the composition is increased to deteriorate workability such as fluidity, and the workability is deteriorated, resulting in a problem of workability.
Even if the filler is blended to the limit, the resin itself as the adhesive layer has low thermal conductivity and does not conduct heat, and the thermal conductivity as a composition is limited.
A method of improving thermal conductivity by using an epoxy resin as a resin used for an adhesive layer and introducing a mesogen structure or the like is disclosed (non-patent document 1). For example, aralkyl type epoxy resins having a biphenyl skeleton are known (patent documents 1, 2, and 3). When these epoxy resins are used, the thermal conductivity is high, but the properties of dielectric constant and dielectric loss tangent are still insufficient due to secondary hydroxyl groups generated during curing.
Under such circumstances, a resin material which is a material having a low dielectric constant and a low dielectric loss tangent and exhibits high thermal conductivity is required.
Documents of the prior art
Patent literature
Patent document 1 Japanese patent laid-open No. 2009-170493
Patent document No. 2
Patent document 3 Japanese patent laid-open publication No. 5-117350
Patent document 4 Japanese patent application laid-open No. 8-143648
Patent document 5 Japanese patent application laid-open No. 8-239454
Non-patent document
Non-patent document 1, national institute of technology, general theory of functionalization of epoxy network polymers based on mesogen skeleton
Disclosure of Invention
The present invention addresses the problem of providing a resin material that has a low dielectric constant, a low dielectric loss tangent, and a high thermal conductivity.
The present inventors have made intensive studies with a view to the resin structure and functional groups, and as a result, have found that the above problems can be solved by a polyfunctional vinyl resin obtained by aromatic vinylating the phenolic hydroxyl group of a polyhydroxy resin having a biphenyl structure in the skeleton and having a tetrafunctional or higher phenolic hydroxyl group, and have completed the present invention.
That is, the present invention relates to a polyfunctional vinyl resin represented by the following general formula (1).
In this case, the amount of the solvent to be used,
x independently represents an aralkyl group having a valence of 2 represented by the following formula (2),
y independently represents an aromatic group having a valence of 2 or more represented by the following formula (3).
Wherein, ar of formula (2) 1 Or Ar of formula (3) 2 At least one of which is a biphenyl ring.
Z independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the following formula (4), and 1 or more of Z are vinyl group-containing aromatic groups.
n represents a repetition number and is an integer of 0 to 15.
m is an integer of 2 or more and independently represents the number of substitution.
-CH 2 -Ar 1 -CH 2 - (2)
-Ar 2 - (3)
-CH 2 -Ar 3 -CH＝CH 2 (4)
In this case, the amount of the solvent to be used,
Ar 1 、Ar 2 、Ar 3 each independently represents an aromatic ring.
The present invention relates to a method for producing a polyfunctional vinyl resin, which is characterized by reacting a polyfunctional phenol compound represented by the following general formula (5) with an aromatic crosslinking agent represented by the following general formula (6) to obtain a polyhydroxy resin represented by the following general formula (7), and then reacting the obtained polyhydroxy resin with an aromatic vinylating agent represented by the following general formula (8).
R 1 -X-R 1 (6)
Z-R 2 (8)
In this case, the amount of the solvent to be used,
x, Y, n and m are each as defined in the above general formula (1).
Z is the same as defined in the above general formula (4).
R 1 Independently represents a halogen group, a hydroxyl group or an alkoxy group.
R 2 Represents a halogen group.
The present invention relates to a polyfunctional vinyl resin composition containing a polyfunctional vinyl resin and, if necessary, a radical initiator, and a polyfunctional vinyl resin cured product obtained by curing the composition.
The present invention also relates to a prepreg comprising a semi-cured product of a polyfunctional vinyl resin composition and a fibrous substrate, a resin sheet provided with a support film, and a laminate obtained by laminating and molding the prepreg or the resin sheet.
The polyfunctional vinyl resin, the composition and the cured product obtained by curing the composition of the present invention have low dielectric constant and dielectric loss tangent, and high thermal conductivity, and are suitable as electronic materials for high-speed communications.
Drawings
FIG. 1 shows the molecular weight distribution (GPC) of the polyhydroxy resin obtained in Synthesis example 3, and the vinyl resin C of example 3 obtained using the same.
Detailed Description
The polyfunctional vinyl resin of the present invention is represented by the above general formula (1).
In the general formula (1), X independently represents a 2-valent aralkyl group represented by the above formula (2), and is a group derived from an aromatic crosslinking agent of a raw material. Ar of formula (2) 1 Is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring and a biphenyl ring.
Y independently represents an aromatic group having a valence of 2 or more represented by the above formula (3), and is a group derived from a polyphenol compound of a raw material. To a 2-valent or 2+m-valent aromatic group. Formula (II)(3)Ar 2 Is an aromatic ring selected from the group consisting of benzene ring, naphthalene ring and biphenyl ring and bisphenol type ring structures.
Wherein, ar of formula (2) 1 Or Ar of formula (3) 2 At least one of them needs to be a biphenyl ring.
Z independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the above formula (4), and 1 or more of the vinyl group-containing aromatic groups are groups derived from an aromatic vinylating agent of a raw material. Ar of formula (4) 3 Is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring and a biphenyl ring.
These aromatic rings Ar 1 、Ar 2 、Ar 3 Are unsubstituted or each independently have 1 or more substituents. The number of the substituent(s) is preferably 1 to 4, and the substituent(s) is preferably an alkyl group or aryl group having 1 to 10 carbon atoms, and more preferably an alkyl group or phenyl group having 1 to 3 carbon atoms.
n represents a repetition number and is an integer of 0 to 15. The average value is 0 to 5.
m is an integer of 2 or more and independently represents the number of substitution. Preferably 2 to 9, more preferably 2 or 3.
The number average molecular weight (Mn) of the polyfunctional vinyl resin of the present invention is preferably 500 to 3000, more preferably 600 to 1500, and the vinyl equivalent is 200 to 500g/eq, more preferably 220 to 350g/eq.
The polyfunctional vinyl resin of the present invention can be suitably obtained by reacting the polyfunctional phenol compound represented by the above general formula (5) with the aromatic crosslinking agent represented by the above general formula (6) to obtain the polyhydroxy resin represented by the above general formula (7), and then reacting the obtained polyhydroxy resin with the aromatic vinylating agent represented by the above general formula (8).
The polyhydroxy resin represented by the general formula (7) is obtained by, for example, reacting a polyfunctional polyphenol compound having two or more functions with an aromatic crosslinking agent such as bishalomethylbiphenyl or bismethoxymethylbiphenyl, but is not limited thereto.
Specific examples of the aromatic crosslinking agent represented by the general formula (6) include 4,4 '-bis (chloromethyl) biphenyl, 4,4' -bis (bromomethyl) biphenyl, dichloroxylene, xylyleneEthylene glycol, xylylene dialkoxy group and isomers thereof, aromatic crosslinking agents having a substituent, and the like. For two R 1 At the substitution position on X, ar of X 1 When it is a benzene ring, it is preferably 1,4-position or 1,3-position, ar of X 1 In the case of a naphthalene ring, it is preferably 1,5-position or 1,6-position, ar of X 1 In the case of a biphenyl ring, the 4,4' -position is preferred. In the aromatic crosslinking agent used, the substitution at these positions is preferably 50 mol% or more.
Examples of the bifunctional or higher polyfunctional phenol compound represented by the general formula (5) include a mononuclear body, a polycyclic aromatic compound, and various bisphenol compounds, and specific examples thereof include the following structures.
As the compounds having various bisphenol structures represented by the above-mentioned last general formula, the following structural examples containing a single bond are given as a connecting group a. Among them, a single bond or an alkylene group having 1 to 3 carbon atoms is preferable. It may have a substituent R 3 When the substituent(s) is (are) 1 to 4, the substituent(s) is (are) preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms.
The bifunctional or higher polyfunctional phenol compound may have a structure represented by the general formula (5), and more preferably includes hydroquinone, 1,4-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 4,4 '-bisphenol, 3,3' -diphenylbisphenol, and the like. For the substitution position of the difunctional hydroxyl group on Y, ar of Y 2 When the aromatic ring is a benzene ring, ar of 1,4-position or 1,3-position, Y is preferred 2 When it is a naphthalene ring, it is preferably 1,5-position or 1,6-position, ar of Y 2 In the case of a biphenyl ring, the 4,4' -position is preferred. In the bifunctional or higher phenol compound used, the substituent at these positions is preferably 50 mol% or more.
The reaction between the bifunctional or higher polyfunctional phenol compound and the aromatic crosslinking agent is carried out in a range of 0.1 to 0.9 mol, preferably 0.15 to 0.85 mol, based on 1 mol of the bifunctional or higher phenol compound.
The reaction of the bifunctional or higher polyfunctional phenol compound with the aromatic crosslinking agent can be synthesized by a known method, that is, preferably, by conducting a condensation reaction in the presence of an acid catalyst while removing by-produced hydrochloric acid, alcohol or water. Specific examples of the acidic catalyst are preferably hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, organic acids, lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride, and particularly p-toluenesulfonic acid, sulfuric acid and hydrochloric acid.
The polyfunctional vinyl resin of the present invention can be suitably obtained by reacting the thus-obtained polyhydroxy resin represented by the general formula (7) with an aromatic vinylating agent represented by the general formula (8).
As the aromatic vinylating agent represented by the general formula (8), halomethylstyrene is preferred. Specific examples of the halomethylstyrene include chloromethylstyrene, bromomethylstyrene and isomers thereof, and a substituted halomethylstyrene. The substitution position of the halomethyl group is preferably the 4-position, and the 4-position is preferably 50 mol% or more of the whole, for example, in the case of halomethylstyrene.
The reaction of the polyhydroxy resin with halomethylstyrene as the aromatic vinylating agent can be carried out in the absence of a solvent or in the presence of a solvent. The reaction may be carried out by adding a halomethylstyrene to the polyhydroxy resin, adding a metal hydroxide to the polyhydroxy resin to carry out the reaction, and removing the resulting metal salt by filtration, washing with water or the like.
Examples of the solvent include, but are not limited to, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, and cyclohexanone. Specific examples of the metal hydroxide include, but are not limited to, sodium hydroxide and potassium hydroxide.
The reaction may be carried out at a temperature of 100 ℃ or lower, preferably 80 ℃ or lower, and when the halomethylstyrene as the aromatic vinylating agent is liable to undergo autopolymerization, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitrosos, nitrols, and oxygen may be used.
The reaction end point can be determined by tracing the remaining amount of the halomethylstyrene as the aromatic vinylating agent with various chromatograms, and the method for adjusting the reaction rate can be adjusted by adjusting the kind and amount of the metal hydroxide, adjusting the addition rate, and using an appropriate catalyst.
The polyfunctional vinyl resin of the present invention can be cured alone, but is preferably used as a polyfunctional resin composition containing various additives.
For example, in order to accelerate curing, curing may be carried out by adding a radical initiator such as an azo compound or an organic peroxide.
The polyfunctional vinyl resin of the present invention may contain other vinyl resins and other thermosetting resins than the above-mentioned resins, and examples thereof include epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzo resins
Oxazine resins, and the like.
The polyfunctional vinyl resin composition may contain a filler such as glass cloth, carbon fiber, alumina, or boron nitride in order to improve thermal conductivity.
For the inorganic filler material as the filler, in order to impart higher thermal conductivity, the higher the thermal conductivity, the better. Preferably 20W/mK or more, more preferably 30W/mK or more, and still more preferably 50W/mK or more. At least a part of the inorganic filler, preferably 50wt% or more, has a thermal conductivity of 20W/m.K or more. Further, the average thermal conductivity as the whole inorganic filler preferably increases in the order of 20W/mK or more, 30W/mK or more, and 50W/mK or more.
Examples of the inorganic filler having such a thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide.
Various additives may be added to improve the adhesion and improve the handling of the composition, and examples thereof include a silane coupling agent, an antifoaming agent, an internal release agent, and a flow control agent.
The polyfunctional vinyl resin or the polyfunctional vinyl resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone, impregnated into a fibrous base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and then heated and dried to obtain a prepreg, which is hot-pressed to obtain a cured product. In this case, the polyfunctional vinyl resin or the polyfunctional vinyl resin composition may be a semi-cured product. Further, a cured product (laminate) having a desired thickness can be produced by laminating a plurality of such prepregs and molding the same. In obtaining the laminate, a cured product that is cured at one time may be combined with a prepreg and molded.
Similarly, a resin layer, which is a semi-cured product of a polyfunctional vinyl resin or a polyfunctional vinyl resin composition, may be applied to a base material (support film) such as a PET film, and the resin layer may be heat-dried or the like to obtain a resin sheet, which is then subjected to hot press molding to obtain a cured product. In addition, as described above, a plurality of such resin sheets may be laminated and molded to form a cured product (laminate) having a desired thickness, and when obtaining the laminate, the cured product that has been cured at one time may be combined with the resin sheets and molded.
Examples
The present invention is described more specifically by examples and comparative examples, and the following are parts by weight unless otherwise specified.
The test conditions of the polyhydroxy resin, vinyl resin and cured product are shown.
(1) Hydroxyl equivalent weight
Using a potentiometric titrator, the solvent was used 1,4-bis
An alkane is acetylated by 1.5mol/L acetyl chloride and then treatedAn amount of acetyl chloride was decomposed with water, and titration was performed using 0.5 mol/L-potassium hydroxide.
(2) Vinyl equivalent weight
The sample was reacted with a wegener's reagent (iodine monochloride solution), left in the dark, and then excess iodine chloride was reduced to iodine, and the iodine content was titrated with sodium thiosulfate to calculate the iodine value. The iodine value is converted to vinyl equivalent.
(3) Total chlorine
The measurement can be carried out by dissolving 1.0g of a sample in 25ml of butyl carbitol, adding 25ml of a 1N-KOH propylene glycol solution, heating under reflux for 10 minutes, cooling to room temperature, further adding 100ml of 80% acetone water, and carrying out potentiometric titration with a 0.002N-AgNO3 aqueous solution.
(4) Molecular weight distribution of resin
The column was analyzed using a GPC measurement apparatus (TOSOH, HLC-8220 GPC), using 1 TSK guard column (TOSOH), 1 TSKgel 2000H XL (TOSOH), 1 TSKgel 3000HXL (TOSOH), 1 TSKgel 4000H XL (TOSOH), RI as a detector, tetrahydrofuran as a solvent, at a flow rate of 1.0mL/min and a column temperature of 40 ℃.
(5) Thermal conductivity
Measured according to JIS R1611.
(6) Dielectric constant and dielectric loss tangent
Measured according to JIS C2138. The measurement frequency is represented by a value of 1 GHz.
Polyhydroxy resin A: the product name BRG-555, manufactured by Aica Kogyo corporation
(Synthesis example 1)
Into a 1000ml 4-neck flask were charged 4,4' -bis (chloromethyl) biphenyl 186.1g, hydroquinone 272.1g, and diethylene glycol dimethyl ether 458.2g, and the temperature was raised to 160 ℃ under nitrogen flow with stirring, followed by reaction for 10 hours. Subsequently, 3g of a 48% potassium hydroxide solution was added thereto, and the reaction was carried out at 130 ℃ for 3 hours. After the reaction, the reaction mixture was dropped into a large amount of purified water, and the mixture was recovered by reprecipitation to obtain 110g of a pale yellow resin. The hydroxyl equivalent weight of the obtained polyhydroxy resin was 110.9g/eq and the total chlorine was 460ppm.
(Synthesis example 2)
The same operation was carried out except for charging 4,4' -bis (chloromethyl) biphenyl 127.9g, 1,6-naphthalenediol 272.1g and diethylene glycol dimethyl ether 400.0g into the same apparatus as in synthesis example 1. The hydroxyl equivalent weight of the obtained polyol resin was 106.8g/eq and the total chlorine was 490ppm.
(Synthesis example 3)
The same operation was carried out except that 140.3g of 4,4 '-bis (chloromethyl) biphenyl, 260.0g of 4,4' -bisphenol and 400.0g of diethylene glycol dimethyl ether were charged into the same apparatus as in synthesis example 1. The hydroxyl group equivalent of the obtained polyhydroxy resin was 128.7g/eq and the total chlorine was 300ppm.
(Synthesis example 4)
The same operation as in Synthesis example 1 was carried out except that 87.5g of p-dichloroxylene, 186g of 4,4 '-dihydroxybiphenyl, 273g of diethylene glycol dimethyl ether as a solvent and 1.37g of p-toluenesulfonic acid as an acid catalyst were charged in place of 4,4' -bis (chloromethyl) biphenyl. The hydroxyl equivalent weight of the obtained polyhydroxy resin was 120.0g/eq and the total chlorine was 420ppm.
(Synthesis example 5)
The same operation was carried out except for charging 4,4' -bis (chloromethyl) biphenyl 87.7g, phenol 94.0g and diethylene glycol dimethyl ether 181.7g into the same apparatus as in synthesis example 1. The hydroxyl equivalent of the obtained polyhydroxy resin was 78.8g/eq and the total chlorine was 360ppm.
(Synthesis example 6)
The same operation was carried out as in Synthesis example 1, except that 87.5g of p-dichloroxylene, 94g of phenol and 182g of diethylene glycol dimethyl ether were charged in the apparatus instead of 4,4' -bis (chloromethyl) biphenyl. The hydroxyl equivalent weight of the obtained polyol resin was 73.0g/eq and the total chlorine was 550ppm.
Example 1
85.0g of the polyol resin obtained in Synthesis example 1, 198.3g of diethylene glycol dimethyl ether, and 117.1g of chloromethyl styrene were charged into the same apparatus as in Synthesis example 1, and the mixture was dissolved by heating to 70 ℃. 87.9g of a 48% aqueous potassium hydroxide solution was added dropwise thereto to carry out a reaction. The absence of chloromethyl styrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized and washed with water to obtain a vinyl resin A. The vinyl equivalent weight of the obtained vinyl resin A was 247.2g/eq and the total chlorine content was 1530ppm.
Example 2
Vinyl resin B was obtained in the same manner as in example 1 except that the polyol resin of Synthesis example 2 was changed to 96.2g, and diethylene glycol dimethyl ether 224.4g, chloromethyl styrene 149.4g, and 48% potassium hydroxide aqueous solution 112.4g, instead of the polyol resin of Synthesis example 1. The vinyl equivalent of the obtained vinyl resin B was 223.5g/eq and the total chlorine was 1670ppm.
Example 3
Vinyl resin C was obtained in the same manner as in example 1 except that the polyol resin of Synthesis example 3 was changed to 104.8g, and diethylene glycol dimethyl ether 231.0g, chloromethyl styrene 129.5g, and 48% potassium hydroxide aqueous solution 100.0g, instead of the polyol resin of Synthesis example 1. The vinyl equivalent of the obtained vinyl resin C was 255.6g/eq and the total chlorine was 1270ppm.
Example 4
Vinyl resin D was obtained in the same manner as in example 1 except that the polyol resin of Synthesis example 4 was changed to 118.6g, and diethylene glycol dimethyl ether (277.1 g), chloromethylstyrene (89.81 g) and 48% potassium hydroxide (86.4 g) were used instead of the polyol resin of Synthesis example 1. The vinyl equivalent weight of the obtained vinyl resin D was 236.8g/eq and the total chlorine was 1300ppm.
Comparative example 1
Vinyl resin E was obtained in the same manner as in example 1 except that the polyol resin of Synthesis example 5 was changed to 118.6g, and diethylene glycol dimethyl ether (277.1 g), chloromethylstyrene (89.81 g) and 48% potassium hydroxide (86.4 g) were used instead of the polyol resin of Synthesis example 1. The vinyl equivalent of the obtained vinyl resin E was 330.5g/eq and the total chlorine was 1680ppm.
Comparative example 2
Vinyl resin F was obtained in the same manner as in example 1 except that the polyol resin A was changed to 95.0g, and diethylene glycol dimethyl ether 221.8g, chloromethyl styrene 145.0g, and 48% potassium hydroxide aqueous solution 121.8g, instead of the polyol resin of Synthesis example 1. The vinyl equivalent of the obtained vinyl resin F was 235.7g/eq and the total chlorine was 1830ppm.
Comparative example 3
Vinyl resin G was obtained in the same manner as in example 1 except that the polyol resin of Synthesis example 6 was changed to 118.6G, and diethylene glycol dimethyl ether 277.1G, chloromethylstyrene 89.81G, and 48% potassium hydroxide aqueous solution 86.4G, instead of the polyol resin of Synthesis example 1. The vinyl equivalent of the obtained vinyl resin G was 192.7G/eq and the total chlorine was 1970ppm.
Examples 5 to 9 and comparative examples 4 to 7
The properties of the resin compositions obtained by mixing the obtained vinyl resins a to G, the resins shown below, an initiator (organic peroxide), and an antioxidant at the mixing ratios shown in table 1, and cured products obtained by curing them are shown.
Vinyl resin H: OPE-2ST, manufactured by Mitsubishi Gas Chemical Co., ltd. (number average molecular weight 1187, vinyl equivalent: 590.0 g/eq)
Organic peroxide: PERBUTYL P RIGHT OIL CO PRODUCED BY CO
Antioxidant: ADK STAB AO-60ADEKA, inc
In examples 5 to 9 and comparative examples 4 to 7, the components were mixed and dissolved in a solvent in the blending ratio shown in table 1 to prepare a uniform composition. This composition was applied to a PET film and dried at 130 ℃ for 5 minutes to obtain a resin composition. The resin composition taken out of the PET film was sandwiched between mirror plates, and cured under reduced pressure at 130 ℃ under a pressure of 15 minutes and 2MPa and at 210 ℃ under a pressure of 80 minutes and 2 MPa.
The values of dielectric constant, dielectric loss tangent and thermal conductivity of the cured product are shown in table 1.
The polyfunctional vinyl resins of the examples exhibited excellent physical properties such as high thermal conductivity, low dielectric constant, and low dielectric loss tangent as compared with those of the comparative examples.
Industrial applicability
The polyfunctional vinyl resin of the present invention is useful as the following materials: when used as an electronic material for high-speed communication equipment, the material is likely to dissipate heat generated from electronic components and wires, thereby reducing signal loss.
Claims (9)
1. A polyfunctional vinyl resin characterized by being represented by the following general formula (1),
in this case, the amount of the solvent to be used,
x independently represents an aralkyl group having a valence of 2 represented by the following formula (2),
y independently represents an aromatic group having a valence of 2 or more represented by the following formula (3),
wherein, ar of formula (2) 1 Or Ar of formula (3) 2 At least one of which is a biphenyl ring,
z independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the following formula (4), and 1 or more of Z are vinyl group-containing aromatic groups,
n represents a repetition number of 0 to 15,
m independently represents the number of substitution, is an integer of 2 or more,
-CH 2 -Ar 1 -CH 2 - (2)
-Ar 2 - (3)
-CH 2 -Ar 3 -CH＝CH 2 (4)
in this case, the amount of the solvent to be used,
Ar 1 、Ar 2 、Ar 3 each independently represents an aromatic ring.
2. The polyfunctional vinyl resin of claim 1 wherein Ar of formula (2) 1 Is an aromatic ring selected from the group consisting of benzene ring, naphthalene ring and biphenyl ring, ar of formula (3) 2 Is selected from benzene ring, naphthalene ring, biphenyl ring and bisphenol typeAromatic ring in the ring structure, ar of formula (4) 3 Is an aromatic ring selected from the group consisting of benzene ring, naphthalene ring and biphenyl ring, and Ar is an aromatic ring 1 、Ar 2 、Ar 3 Are unsubstituted or each independently may have 1 or more substituents.
3. A process for producing a polyfunctional vinyl resin according to claim 1, which comprises reacting a polyfunctional phenol compound represented by the following general formula (5) with an aromatic crosslinking agent represented by the following general formula (6) to obtain a polyhydroxy resin represented by the following general formula (7), and then reacting the obtained polyhydroxy resin with an aromatic vinylating agent represented by the following general formula (8),
R 1 -X-R 1 (6)
Z-R 2 (8)
in this case, the amount of the solvent to be used,
x, Y, n and m are respectively the same as the definitions in the general formula (1),
z is as defined in said general formula (4),
R 1 independently represents halogen, hydroxy or alkoxy,
R 2 represents halogen.
4. A polyfunctional vinyl resin composition comprising the polyfunctional vinyl resin of claim 1 and a radical polymerization initiator as essential components.
5. A cured product of a polyfunctional vinyl resin obtained by curing the polyfunctional vinyl resin according to claim 1 or the polyfunctional vinyl resin composition according to claim 4.
6. A prepreg comprising the polyfunctional vinyl resin according to claim 1, the polyfunctional vinyl resin composition according to claim 4, or a semi-cured product thereof and a fibrous substrate.
7. A resin sheet comprising a resin layer of the polyfunctional vinyl resin according to claim 1, the polyfunctional vinyl resin composition according to claim 4, or a prepreg thereof, and a support film.
8. A laminate obtained by laminating and molding the prepreg according to claim 6.
9. A laminated plate obtained by laminating and molding the resin sheet according to claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020060282 | 2020-03-30 | ||
| JP2020-060282 | 2020-03-30 | ||
| PCT/JP2021/012081 WO2021200414A1 (en) | 2020-03-30 | 2021-03-23 | Polyfunctional vinyl resin and production method therefor |
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| CN115362194A true CN115362194A (en) | 2022-11-18 |
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| JP (1) | JPWO2021200414A1 (en) |
| CN (1) | CN115362194A (en) |
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| WO2024071047A1 (en) * | 2022-09-29 | 2024-04-04 | 日鉄ケミカル＆マテリアル株式会社 | Polyfunctional vinyl resin, and production method, composition, and cured product of same |
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| JP4591946B2 (en) * | 2004-04-28 | 2010-12-01 | 日本化薬株式会社 | Poly (vinylbenzyl) ether compound and process for producing the same |
| JP5002897B2 (en) * | 2005-03-08 | 2012-08-15 | Ｄｉｃ株式会社 | Polyhydric hydroxy compound, epoxy resin, production method thereof, epoxy resin composition and cured product |
| WO2014103926A1 (en) * | 2012-12-27 | 2014-07-03 | 新日鉄住金化学株式会社 | Poly(vinyl benzyl) ether compound, method for producing same, curable composition containing same, and cured article |
| KR102010802B1 (en) * | 2013-02-05 | 2019-08-14 | 닛뽄 가야쿠 가부시키가이샤 | Allyl ether resin and epoxy resin |
| CN106795276B (en) * | 2014-07-01 | 2019-09-24 | 明和化成株式会社 | Allyl ether or the modified biphenyl aralkyl novolac resin of allyl, its manufacturing method and the composition for having used it |
| JP6605828B2 (en) * | 2015-03-30 | 2019-11-13 | 日鉄ケミカル＆マテリアル株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
| JP6755643B2 (en) * | 2015-07-29 | 2020-09-16 | 明和化成株式会社 | Allyl ether-modified biphenyl aralkyl novolac resin, allyl-modified biphenyl aralkyl novolac resin, a method for producing the same, and a composition using the same. |
| JP6808318B2 (en) * | 2015-12-28 | 2021-01-06 | 日鉄ケミカル＆マテリアル株式会社 | Manufacturing method of multivalent hydroxy resin and epoxy resin |
| TW201800437A (en) * | 2016-03-01 | 2018-01-01 | 新日鐵住金化學股份有限公司 | Poly(vinylbenzyl)ether compound, curable resin composition containing this and cured article |
| TWI728084B (en) * | 2016-03-30 | 2021-05-21 | 日商日鐵化學材料股份有限公司 | Polyvalent hydroxy resin, its manufacturing method, epoxy resin, epoxy resin composition and its hardened product |
| JP6319703B1 (en) * | 2017-07-11 | 2018-05-09 | 群栄化学工業株式会社 | Propenyl group-containing resin, resin composition, resin varnish, laminate manufacturing method, thermosetting molding material and sealing material |
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