JP2010275557A - Novel thermosetting benzoxazine resin and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin that has toughness in addition to high flexibility and also has high reliability as a thermosetting resin, a suitable method for manufacturing the same, and a cured product obtained by curing the resin. <P>SOLUTION: The thermosetting benzoxazine resin having a phenoxy moiety in the skeleton and a suitable method for manufacturing the same are provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel thermosetting benzoxazine resin having a specific skeleton structure, and particularly relates to a thermosetting benzoxazine resin which exhibits excellent high flexibility and toughness and is suitable for electronic parts and the like.

  The present invention also provides a suitable method for producing the thermosetting benzoxazine resin, a cured product obtained by curing the thermosetting benzoxazine resin, a resin composition containing the thermosetting benzoxazine resin, and the heat The present invention relates to a metal-clad laminate obtained from a curable benzoxazine resin.

  Thermosetting resins are, for example, electronic parts that require high reliability because the cross-linked structure unique to thermosetting resins such as thermosetting benzoxazine resin expresses high heat resistance and dimensional stability. Widely used in the field. However, this cross-linked structure also has a drawback that it reduces the flexibility and toughness of the cured resin. Therefore, when thermosetting resin is used for electronic parts, there are problems such as cracks occurring when drilling or punching is performed, and the shape of the processed part such as drilling is deteriorated. Often occurs.

  As examples of thermosetting benzoxazine resins, for example, Patent Documents 1 to 19 include a method for producing a dihydrobenzoxazine resin from a phenol compound, an aldehyde, and an amine compound in addition to various dihydrobenzoxazine resins. It is disclosed. Patent Documents 1 to 15 describe poly (dihydrobenzoxazine), a structure in which the benzoxazine moiety has a substituent such as alkyl or phenyl, and two or more benzoxazine moieties are alkyl or carbonyl. , Silanol, oxygen, sulfur and the like are described. Patent Documents 16 to 18 include a condensed tricyclic structure in which a benzoxazine moiety and another aromatic ring are combined, and a structure containing pendant functional groups such as isocyano, isocyanato, carbonyl, silanol, isoxazolyl, alkenyl, and alkynyl. Is described. Patent Document 19 describes a structure in which dioxyl and aminoxyl are bonded to a dioxazine moiety via alkyl or alkenyl.

  However, the cured products using the thermosetting benzoxazine resin described in these Patent Documents 1 to 19 or the electronic parts using the same are acceptable in the fine processing and wiring formation required today. Thermosetting benzoxazine resin, which has problems such as cracking when drilling or punching is performed, and the shape of the processed part is degraded, such as drilling or punching. It does not solve unique problems.

  Thus, there is a need for a novel thermosetting benzoxazine resin that has toughness in addition to flexibility. In the production of a thermosetting benzoxazine resin, the selection of starting materials is important. A factor that determines whether or not a thermosetting benzoxazine resin capable of solving the above problems can be produced is the selection of the combination of starting materials. Therefore, in order to obtain a novel benzoxazine resin, a search for starting materials has been conducted.

JP-A-60-155234 JP-A-60-177199 JP-A-8-183837 JP-A-9-59334 JP-A-9-502252 JP 10-25343 A JP 11-12258 A JP-A-11-263780 JP-A-11-279309 JP 2000-17146 A JP 2000-169456 A JP 2000-34339 JP 2001-19844 JP 2001-64480 A JP 2001-271070 A Special table 2001-519342 JP 2002-226536 A JP 2002-241495 A JP 2002-302486 A

  An object of the present invention is to provide a thermosetting benzoxazine resin having toughness in addition to excellent flexibility and suitable for electronic parts and the like.

  The present invention is a thermosetting benzoxazine resin having a phenoxy moiety in the skeleton.

  The present invention is a thermosetting benzoxazine resin further having a hydroxypropylene moiety in addition to a phenoxy moiety in the skeleton.

  The present invention is directed to general formula (I):

（Ｉ）

(I)

(Where
R ¹ and R ² are each independently a hydrocarbon group having 1 to 9 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group;
A is absent or a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group, or a sulfonyl group;
D is the following group:

（Ｄ）

(D)

Where A is as defined above;
m is 0 or a positive integer)
It is preferable to contain at least 1 type of thermosetting benzoxazine resin shown by these. The aromatic ring in the above formula may be substituted, and examples of the substituent include an alkyl group and a cycloalkyl group.

  The present invention relates to general formula (II):

（II）

(II)

(Where
R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 9 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group;
E and J are each independently absent or a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group, and a sulfonyl group;
G is a group:

（Ｇ）

(G)

Where E and J are as defined above;
n is 0 or a positive integer)
It is preferable that at least 1 type of thermosetting benzoxazine resin shown by these is included. The aromatic ring in the above formula may be substituted, and examples of the substituent include an alkyl group and a cycloalkyl group.

  The production method of the present invention has the general formula (III):

（III）

(III)

(Where
Each E is independently absent or a linear hydrocarbon group having 1 to 5 carbon atoms, isopropylidene group, oxygen atom, carbonyl group, sulfonyl group;
L is a group:

（Ｌ）

(L)

Wherein J is absent or is a linear hydrocarbon group having 1 to 5 carbon atoms, isopropylidene group, oxygen atom, carbonyl group, sulfonyl group; E is Synonymous with the above;
p is a positive integer)
A polyether having a phenol ring terminal represented by
An aldehyde,
This is a method for producing a thermosetting benzoxazine resin in which at least one primary amine compound is reacted.

  In the production method of the present invention, the polyether having a phenol ring represented by the general formula (III) at the terminal is represented by the general formula (IV):

(IV)

(IV)

(Where E is as defined above)
A bifunctional phenol compound represented by:
Formula (V):

（Ｖ）

(V)

(Wherein J is as defined above)
Is a method for producing a thermosetting benzoxazine resin in which a polyhydroxypropyl etherification reaction is performed with a bifunctional epoxy compound.

  Furthermore, the present invention is characterized by being produced by reacting a polyether having a phenol ring represented by the above general formula (III), an aldehyde, and one or more primary amine compounds. A thermosetting benzoxazine resin.

  According to the present invention, a thermosetting resin having toughness in addition to good flexibility and excellent in heat resistance and adhesiveness with copper foil can be obtained and used for electronic parts and the like. A thermosetting resin having high reliability can be obtained.

Hereinafter, the present invention will be described in detail.
The present invention is a thermosetting benzoxazine resin having a novel structure.

R ¹ and R ² in the general formula (I) are each independently a hydrocarbon group having 1 to 9 carbon atoms and an aromatic hydrocarbon group which may be unsubstituted or substituted.

The number one to nine hydrocarbon group of carbon atoms of the ^{R 1} and ^{R 2} in the general formula (I), for example of 1-9 carbon atoms, alkyl, alkenyl, ether and the like. Examples of the alkyl having 1 to 9 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl. Examples of the alkenyl having 1 to 9 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and nonylene. Examples of ethers include aliphatic single ethers, aliphatic hybrid ethers, and aliphatic unsaturated ethers. Examples of the aliphatic single ether having 1 to 9 carbon atoms include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and the like. Examples of the aliphatic mixed ether having 1 to 9 carbon atoms include methyl ethyl ether, methyl propyl ether, methyl butyl ether, ethyl propyl ether ethyl butyl ether, ethyl amyl ether and the like. Examples of the aliphatic unsaturated ether having 1 to 9 carbon atoms include vinyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, and ethyl allyl ether. The number one to nine hydrocarbon group of carbon atoms of the R ¹ and R ² in the general formula (I), ethyl ether and methylene is preferable.

Examples of the aromatic hydrocarbon group for R ¹ and R ² in the general formula (I) include phenyl, cumenyl, mesityl, tolyl, xylyl, phenylene, benzyl, phenethyl, benzhydryl, styryl, cinnamyl, trityl, naphthyl and the like. Phenyl is preferred.

  A in the general formula (I) does not exist or is a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group, or a sulfonyl group, and has 1 to 5 carbon atoms. It is preferably a straight-chain hydrocarbon group or isopropylidene group.

  As a C1-C5 linear hydrocarbon group about A of general formula (I), a C1-C5 alkyl, alkenyl, ether is mentioned, for example. Examples of the alkyl having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl and pentyl. Examples of the alkenyl having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene, and pentylene. Examples of ethers include aliphatic single ethers, aliphatic hybrid ethers, and aliphatic unsaturated ethers. Examples of the aliphatic single ether having 1 to 5 carbon atoms include methyl ether, ethyl ether, propyl ether, butyl ether, and amyl ether. Examples of the aliphatic mixed ether having 1 to 5 carbon atoms include methyl ethyl ether, methyl propyl ether, methyl butyl ether, and ethyl propyl ether. Examples of the aliphatic unsaturated ether having 1 to 5 carbon atoms include vinyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, and ethyl allyl ether. As the linear hydrocarbon group having 1 to 5 carbon atoms for A and B in the general formula (I), ethyl ether and methylene are preferable.

Examples of R ³ and R ⁴ for the general formula (II) of the present invention are the same as those of R ¹ and R ² for the general formula (I) of the present invention.

  Examples of linear hydrocarbon groups having 1 to 5 carbon atoms for E and J in the general formula (II) of the present invention are those having 1 to 5 carbon atoms for A in the general formula (I) of the present invention. This is the same as the illustration of the linear hydrocarbon group.

  A preferred embodiment of the general formula (II) of the present invention is a case where n is 0 in the general formula (II), and the following formula (VI):

（VI）
（式中、
Ｒ³及びＲ⁴は、それぞれ独立して、炭素数１〜９個の炭化水素基、非置換又は置換されていてもよい芳香族炭化水素基であり、好ましくは炭素数１〜９個のアルキレン基、非置換又は置換されていてもよいフェニル基であり；
Ｅは、存在しないか、又は炭素数１〜５個の直鎖状の炭化水素基、イソプロピリデン基、酸素原子、カルボニル基、スルホニル基であり、好ましくは炭素数１〜５個の直鎖状の炭化水素基、イソプロピリデン基であり、より好ましくは、エーテル部分を有する炭素数１〜５個の直鎖状の炭化水素基、炭素数１〜５個のアルキレン基、イソプロピリデン基であり；
Ｊは、存在しないか、又は炭素数１〜５個の直鎖状の炭化水素基、イソプロピリデン基、酸素原子、カルボニル基、スルホニル基であり、好ましくは炭素数１〜５個の直鎖状の炭化水素基、イソプロピリデン基であり、より好ましくは、炭素数１〜５個のアルキレン基、イソプロピリデン基である）
で示される化合物である。

(VI)
(Where
R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 9 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group, preferably an alkylene having 1 to 9 carbon atoms. A phenyl group which may be unsubstituted or substituted;
E is not present or is a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group or a sulfonyl group, preferably a linear chain having 1 to 5 carbon atoms A hydrocarbon group and an isopropylidene group, more preferably a linear hydrocarbon group having 1 to 5 carbon atoms having an ether moiety, an alkylene group having 1 to 5 carbon atoms, and an isopropylidene group;
J is not present or is a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group, or a sulfonyl group, preferably a linear chain having 1 to 5 carbon atoms A hydrocarbon group and an isopropylidene group, more preferably an alkylene group having 1 to 5 carbon atoms and an isopropylidene group)
It is a compound shown by these.

  According to the production method of the present invention, a thermosetting benzoxazine resin, a polyether having a phenol ring represented by the general formula (III) as a terminal, an aldehyde, and one or more primary amine compounds, It can be produced by reacting and converting all or part of the terminal phenol ring to a dihydrobenzoxazine ring.

  Specifically, an aldehyde and a primary amine compound are dropped in small amounts sequentially into a polyether having a phenol ring represented by the general formula (III) or a product obtained by uniformly dissolving the phenol ring in a solvent. A thermosetting benzoxazine resin represented by the general formula (I) or (II) can be obtained by reacting at a temperature of 0 ° C. or higher for 0.5 to 10 hours.

  Examples of the linear hydrocarbon group having 1 to 5 carbon atoms for E and J in the general formulas (III) and (IV) of the present invention include, for example, alkyl, alkenyl and ether having 1 to 5 carbon atoms. Can be mentioned. Examples of the alkyl having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl and pentyl. Examples of the alkenyl having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene, and pentylene. Examples of the ether having 1 to 5 carbon atoms include aliphatic single ethers, aliphatic hybrid ethers, and aliphatic unsaturated ethers. Examples of the aliphatic single ether having 1 to 5 carbon atoms include methyl ether, ethyl ether, propyl ether, butyl ether, and amyl ether. Examples of the aliphatic mixed ether having 1 to 5 carbon atoms include methyl ethyl ether, methyl propyl ether, methyl butyl ether, and ethyl propyl ether. Examples of the aliphatic unsaturated ether having 1 to 5 carbon atoms include vinyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, and ethyl allyl ether. As the linear hydrocarbon group having 1 to 5 carbon atoms for E and J in the general formulas (III) and (IV), ethyl ether and methylene are preferable.

  According to the production method of the present invention, a polyether having a phenol ring represented by the general formula (III) at its terminal is converted into a bifunctional phenol compound (for example, a bifunctional phenol compound represented by the general formula (IV)) and 2 A functional epoxy compound (for example, a bifunctional epoxy compound represented by the general formula (V)), and an organic solvent and a reaction catalyst, if necessary, are obtained by reacting at 70 ° C. or higher for 0.5 to 10 hours. .

  Examples of the bifunctional phenol compound represented by the general formula (IV) include bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenyl, and the like, and may be hydroquinone or naphthalenediol. Among these, bisphenol A, bisphenol F, dihydroxydiphenyl ether, and dihydroxydiphenyl, which have a high cyclization reaction rate of the benzoxazine ring and can achieve higher flexibility and higher heat resistance, are preferred, and bisphenol A, bisphenol F, and dihydroxydiphenyl ether are preferred. Bisphenol A and bisphenol F are particularly preferred because they are more preferred and inexpensive.

  Examples of the bifunctional epoxy compound represented by the general formula (V) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, and the like, and also a bifunctional naphthalene ring. Other bifunctional epoxy compounds such as a contained epoxy resin may be used. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin that can be made more flexible and heat resistant are more preferable.

  A polyether having a phenol ring represented by the general formula (III) as a terminal comprises a bifunctional phenol compound represented by the general formula (IV) and a bifunctional epoxy compound represented by the general formula (V). It is preferable to obtain it by blending so that the hydroxyl equivalent a of the bifunctional phenolic compound is greater than the epoxy equivalent b of the bifunctional epoxy compound, and causing polyhydroxypropyl etherification reaction. The value of the hydroxyl equivalent a of the bifunctional phenol compound is preferably 90 to 125, and more preferably 95 to 120. The value of the epoxy equivalent b of the bifunctional epoxy compound is preferably 155 to 205, and more preferably 160 to 200. From the point of toughness in addition to high flexibility, the blending ratio of the hydroxyl equivalent a of the bifunctional phenol compound and the epoxy equivalent b of the bifunctional epoxy compound is in the range of a / b = 5/1 to 3/2. In view of the rate of formation of the dihydrobenzoxazine ring during the synthesis of the benzoxazine resin (cyclization reaction rate), it is more preferable that the ratio be in the range of a / b = 5/1 to 4/3, From the viewpoint of heat resistance, it is particularly preferable that the ratio is in the range of a / b = 3/1 to 4/3.

  In the reaction for producing a polyether having a phenol ring represented by the general formula (III) as an end, an organic solvent can be arbitrarily used as necessary. Examples of organic solvents include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, and aromatic solvents such as toluene, xylene, and mesitylene. Group solvents, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned, and one kind or a mixture of two or more kinds can be used.

  In the reaction for producing a polyether having a phenol ring represented by the general formula (III) as a terminal, a reaction catalyst can be optionally used as necessary. Examples of reaction catalysts include, but are not limited to, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and 2-phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Or 2 or more types can be mixed and used.

  Examples of the aldehyde used in the production of the thermosetting benzoxazine resin of the present invention include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, pivalinaldehyde, and heptoaldehyde, and formaldehyde is preferable. The aldehyde is preferably used as an aqueous solution, for example, an aqueous solution having a concentration of about 35% by weight or more. Moreover, in order to increase the solubility of said aldehyde, about 10-15% of alcohol like methanol can be contained in this aqueous solution, for example. Commercially available formalin can be used as the aldehyde used in the production of the thermosetting benzoxazine resin of the present invention.

  As a primary amine compound used for manufacture of the thermosetting benzoxazine resin of this invention, 1 or more types of amine compounds chosen from a C1-C9 aliphatic primary amine and aromatic amine are preferable. Examples of the aliphatic primary amine having 1 to 9 carbon atoms include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine and nonylamine, and methylamine is preferable. Examples of the aromatic amine having 1 to 9 carbon atoms include aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, o-toluidine, m-toluidine, p-toluidine, benzylamine, dibenzylamine, and tribenzylamine. , Diphenylamine, triphenylamine, α-naphthylamine, β-naphthylamine, and aniline and methylaniline are preferred. As the primary amine compound, methylamine, aniline, methylaniline and the like are preferable, and among them, aniline which has a high cyclization reaction rate of the benzoxazine ring and can be made more flexible and heat resistant is particularly preferable.

  The hardened | cured material of this invention is a hardened | cured material obtained by hardening | curing said thermosetting benzoxazine resin or the thermosetting benzoxazine resin obtained by said manufacturing method.

  The thermosetting benzoxazine resin of the present invention can be heated and cured at a temperature of 160 ° C. or higher, preferably 180 to 230 ° C. for 30 minutes or longer to obtain an aminoalkyl represented by J. Org. Chem., 30.3423 (1965), etc. The reaction can be completed and a desired cured product can be obtained. In order to cure the thermosetting benzoxazine resin of the present invention, it is preferable to fill the resin in a mold or the like, and to perform heat molding under the above conditions by a casting method or the like.

  A cured product obtained by curing the thermosetting benzoxazine resin of the present invention is excellent in flexibility, and also excellent in basic characteristics as a thermosetting resin such as heat resistance.

  The resin composition of the present invention is a thermosetting benzoxazine resin composition containing the above thermosetting benzoxazine resin or the thermosetting benzoxazine resin obtained by the above production method.

  The thermosetting benzoxazine resin of the present invention can be added with a filler, an additive and the like within the scope of the object of the present invention, and can be used as a resin composition in combination with other resins. And the thermosetting benzoxazine resin of the present invention or the resin composition containing the same can be molded into a desired shape according to the application to be used, and is combined with the base material as a curable composite material (and its cured product) ) Can be optionally formed as a laminate.

  The filler used in the present invention may be fibrous or powdery, for example, carbon black, silica, alumina, barium titanate, talc, mica, glass beads, glass hollow sphere, glass fiber, carbon Examples thereof include fibers, silica salts such as calcium silicate, metal hydroxides such as aluminum hydroxide, and carbonates such as calcium carbonate.

  Examples of the additive used in the present invention include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a coupling agent, a pigment, a dye, a colorant, and rubber.

  Examples of other resins used for forming the resin composition in the present invention include thermosetting resins such as epoxy resins, novolac-type phenol resins, and melamine resins. In addition, crosslinkable monomers such as triallyl isocyanurate, triallyl cyanurate allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, polyethylene, polypropylene, polybutene, ethylene-polypropylene copolymer, nylon (registered trademark) 4, nylon (registered) (Trademark) 6, Nylon (registered trademark) 6, 6, polyethylene terephthalate, polycarbonate, polyacetal, polysulfone, polyvinyl chloride, polystyrene, and other thermoplastic resins can also be used.

  The metal-clad laminate of the present invention is a metal-clad laminate obtained by using the above thermosetting benzoxazine resin, the thermosetting benzoxazine resin obtained by the above production method, or the above resin composition. .

  The metal-clad laminate of the present invention is produced using the above thermosetting benzoxazine resin, the thermosetting benzoxazine resin obtained by the above production method, or the above resin composition, for example, as follows. can do. A metal-clad laminate can be formed by impregnating a base material with the resin or resin composition of the present invention to form a prepreg, and laminating a copper foil on one side or both sides of the obtained prepreg. Thereafter, the copper foil can be arbitrarily processed to form a desired pattern to form a circuit. A prepreg and / or copper foil or a circuit can be further laminated on such a single-sided or double-sided circuit board to form a multilayer laminated board.

  As the base material used in the present invention, various glass cloths or glass nonwoven fabrics such as roving cloth, cloth, chopped mat, and surfing mat; ceramic fiber cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber, Woven or non-woven fabric obtained from synthetic fibers such as polyester fiber, acrylic fiber, wholly aromatic polyamide fiber; natural fiber fabric such as cotton cloth, linen cloth, felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass mixed paper Natural cellulose-based cloths, etc. can be used, and each can be used alone or in combination of two or more.

  Applications of the thermosetting benzoxazine resin of the present invention include automobile parts, electronic / electric parts, kitchen parts, and the like. Examples of the electronic / electrical component include circuit board laminate materials and semiconductor sealing materials.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples are not intended to limit the present invention in any way.

Example 1 Production of Thermosetting Benzoxazine Resin (1-1) Bifunctional phenolic compound in a 1 liter reaction vessel having a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. Bisphenol A (hydroxyl equivalent: 114) 142.37 g, bisphenol A type epoxy resin as bifunctional epoxy compound (trade name YD-8125 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 172) 107.40 g, and organic 166.52 g of toluene as a solvent and 83.26 g of cyclohexanone were added, and the mixture was heated to 100 ° C. and dissolved uniformly. After dissolution, 0.45 g of 2-phenylimidazole as a reaction catalyst was added little by little, and the reaction was performed at 120 ° C. for 8 hours after the addition. Thereafter, the mixture was cooled to about 35 ° C., and 104.07 g of a 36 wt% formalin solution as an aldehyde and 58.07 g of aniline as a primary amine compound were successively added dropwise. After the addition, the temperature was raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (1-1).
Resin (1-1) has a blending ratio of a hydroxyl equivalent of a bifunctional phenolic compound a and an epoxy equivalent b of a bifunctional epoxy compound of a / b = 2.0. A and B are isopropylidene groups, substituents R ¹ and R ² are phenyl groups, and formation of a dihydrobenzoxazine ring was confirmed by absorption at 900 to 1000 cm ⁻¹ by performing FT-IR measurement.
The obtained thermosetting benzoxazine resin (1-1) was subjected to a property test of the cured product, and the results are shown in Table 1.

Characteristic test of cured product Each obtained thermosetting benzoxazine resin was filled in a mold having an internal volume of 100 × 100 × 1 mm, and heated with a hydraulic press device at 180 ° C. for 1 hour-1.5 MPa. Pressure was applied to obtain a plate-shaped molded product. This was cut appropriately and subjected to a bending test and a solder heat resistance test.
In addition, 18 μm electrolytic copper foils were placed on the obtained plate-shaped molded product, and heated and pressed in the same manner to produce a copper-clad molded product, which was used for the adhesion (peel strength) test.
The results are shown in Table 1.

(1) Bending test The bending test was performed about three items, bending strength, a bending elastic modulus, and a bending fracture strain rate. The measurement was performed by a three-point bending test under conditions of 20 mm between fulcrums and a bending speed of 2 mm / min.

(2) Solder heat resistance test After being immersed in a solder bath having a temperature of 288 ° C for 20 seconds, the solder heat resistance was evaluated by observing the appearance. Evaluation was good: no abnormality in appearance, and blistering: blistering.

(3) Evaluation of adhesiveness (peel strength) By immersing a copper-clad molded article in a copper etching solution, a 1 cm wide copper foil is formed to produce a test piece, and a tensile tester is used to make the copper foil Adhesiveness (peel strength) was measured.

Example 2 Production of thermosetting benzoxazine resin (1-2) Bifunctional phenolic compound in a 1 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling Bisphenol A (hydroxyl equivalent: 114) 124.51 g as a bifunctional epoxy compound, bisphenol A type epoxy resin (trade name YD-8125, epoxy equivalent: 172 manufactured by Tohto Kasei Co., Ltd.) 125.23 g, and organic 166.49 g of toluene as a solvent and 83.25 g of cyclohexanone were added, and the mixture was heated to 100 ° C. and dissolved uniformly. After dissolution, 0.52 g of 2-phenylimidazole as a reaction catalyst was added little by little, and the reaction was performed at 120 ° C. for 8 hours after the addition. Thereafter, it is cooled to about 35 ° C., 60.68 g of a 36 wt% formalin solution as an aldehyde, and 33.86 g of aniline as a primary amine compound are successively added dropwise. After the addition, the temperature is raised to 80 ° C. for 7 hours. Reaction was performed. Then, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (1-2).
Resin (1-2) has a mixing ratio of hydroxyl equivalent a of the bifunctional phenolic compound and epoxy equivalent b of the bifunctional epoxy compound of a / b = 1.5, and in general formula (I), the bonding group A and B are isopropylidene groups, substituents R ¹ and R ² are phenyl groups, and formation of a dihydrobenzoxazine ring was confirmed by absorption at 900 to 1000 cm ⁻¹ by performing FT-IR measurement.
The obtained thermosetting benzoxazine resin (1-2) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 1.

Example 3 Production of thermosetting benzoxazine resin (1-3) Bifunctional phenolic compound in a 1 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. 4.4'-dihydroxydiphenyl ether (hydroxyl equivalent: 101) 134.90 g as a bifunctional epoxy compound (trade name YD-8125, product name YD-8125, manufactured by Tohto Kasei Co., Ltd.) 114 .86 g, 166.50 g of toluene as an organic solvent, and 83.25 g of cyclohexanone were added, and the mixture was heated to 100 ° C. and uniformly dissolved. After dissolution, 0.48 g of 2-phenylimidazole as a reaction catalyst was added little by little, and the reaction was performed at 120 ° C. for 8 hours after the addition. Thereafter, the mixture was cooled to about 35 ° C., and 111.30 g of a 36 wt% formalin solution as an aldehyde and 62.11 g of aniline as a primary amine compound were successively added dropwise. After the addition, the temperature was raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (1-3).
Resin (1-3) has a mixing ratio of hydroxyl equivalent a of the bifunctional phenol compound and epoxy equivalent b of the bifunctional epoxy compound of a / b = 2.0. In general formula (I), the bonding group A is an ethyl ether group, the linking group B is an isopropylidene group, the substituents R ¹ and R ² are phenyl groups, and the formation of the dihydrobenzoxazine ring is 900 to 1000 cm ⁻¹ by performing FT-IR measurement. Was confirmed by absorption.
The obtained thermosetting benzoxazine resin (1-3) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 1.

Example 4 Production of thermosetting benzoxazine resin (1-4) A bifunctional phenol compound was added to a reaction vessel having a thermometer, a stirrer, a moisture meter with a reflux condenser and a heat-coolable volume of 1 liter. Bisphenol F (hydroxyl equivalent: 100) 135.37 g as a bifunctional epoxy compound (product name: Epicoat 807, epoxy equivalent: 169) 114.39 g as a bifunctional epoxy compound, In addition, 166.50 g of toluene as an organic solvent and 83.25 g of cyclohexanone were added, and the mixture was heated to 100 ° C. and uniformly dissolved. After dissolution, 0.49 g of 2-phenylimidazole as a reaction catalyst was added little by little, and the reaction was performed at 120 ° C. for 8 hours after the addition. Thereafter, the mixture was cooled to about 35 ° C., and 112.80 g of a 36 wt% formalin solution as an aldehyde and 62.95 g of aniline as a primary amine compound were successively added dropwise. After the addition, the temperature was raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (1-4).
Resin (1-4) has a blending ratio of hydroxyl equivalent a of the bifunctional phenolic compound and epoxy equivalent b of the bifunctional epoxy compound of a / b = 2.0. A and B are methylene groups, substituents R ¹ and R ² are phenyl groups, and formation of a dihydrobenzoxazine ring was confirmed by absorption at 900 to 1000 cm ⁻¹ by FT-IR measurement.
The obtained thermosetting benzoxazine resin (1-4) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 1.

Example 5 Production of thermosetting benzoxazine resin (1-5) A bifunctional phenol compound was added to a reaction vessel having a thermoliter, a stirrer, and a water quantifier equipped with a reflux condenser with a volume of 1 liter capable of being heated and cooled. Bisphenol A (hydroxyl equivalent: 114) 166.22 g as a bifunctional epoxy compound (trade name YD-8125, epoxy equivalent: 172, manufactured by Tohto Kasei Co., Ltd.) 83.60 g, and organic 166.55 g of toluene as a solvent and 83.27 g of cyclohexanone were added, and the mixture was heated to 100 ° C. and uniformly dissolved. After dissolution, 0.35 g of 2-phenylimidazole as a reaction catalyst was added little by little, and the reaction was performed at 120 ° C. for 8 hours after the addition. Thereafter, the mixture was cooled to about 35 ° C., and 162.01 g of a 36 wt% formalin solution as an aldehyde and 90.40 g of aniline as a primary amine compound were successively added dropwise. After the addition, the temperature was raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (1-5).
Resin (1-5) has a blending ratio of the hydroxyl equivalent a of the bifunctional phenol compound to the epoxy equivalent b of the bifunctional epoxy compound of a / b = 3.0. A and B are isopropylidene groups, substituents R ¹ and R ² are phenyl groups, and formation of a dihydrobenzoxazine ring was confirmed by absorption at 900 to 1000 cm ⁻¹ by performing FT-IR measurement.
The obtained thermosetting benzoxazine resin (1-5) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 1.

Example 6 Production of thermosetting benzoxazine resin (1-6) Bifunctional phenolic compound in a 1 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling Bisphenol F (hydroxyl equivalent: 100) 127.11 g as a bifunctional epoxy compound (trade name YX-4000H epoxy equivalent: 193, manufactured by Dainippon Ink Co., Ltd.) 122.66 g, and organic solvent 166.51 g of toluene and 83.26 g of cyclohexanone were added, and the mixture was heated to 100 ° C. and uniformly dissolved. After dissolution, 0.46 g of 2-phenylimidazole as a reaction catalyst was added little by little, and the reaction was performed at 120 ° C. for 8 hours after the addition. Thereafter, it is cooled to about 35 ° C., and 105.92 g of a 36 wt% formalin solution as an aldehyde and 59.11 g of aniline as a primary amine compound are successively added dropwise, and after the addition, the temperature is raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (1-6).
Resin (1-6) has a blending ratio of hydroxyl equivalent a of the bifunctional phenolic compound and epoxy equivalent b of the bifunctional epoxy compound of a / b = 2.0. A is a methylene group and the linking group B does not exist. Also, substituents ^{R 1} and ^{R 2} are phenyl groups, the formation of dihydrobenzoxazine rings was confirmed by absorption of 900～1000Cm ^-1 performed FT-IR measurement.
The obtained thermosetting benzoxazine resin (1-6) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 1.

Comparative Example 1 Production of thermosetting benzoxazine resin (2-1) Bifunctional phenolic compound in a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling And 250.00 g of bisphenol A (hydroxyl equivalent: 114) as an organic solvent, 166.67 g of toluene as an organic solvent and 83.33 g of cyclohexanone, were heated to 100 ° C. and uniformly dissolved. Thereafter, it is cooled to about 35 ° C., 365.50 g of a 36 wt% formalin solution as an aldehyde and 203.95 g of aniline as a primary amine compound are successively added dropwise, and after the addition, the temperature is raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (2-1).
Formation of the dihydrobenzoxazine ring was confirmed by absorption at 900 to 1000 cm ⁻¹ by performing FT-IR measurement.
The obtained thermosetting benzoxazine resin (2-1) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 2.

Comparative Example 2 Production of thermosetting benzoxazine resin (2-2) Bifunctional phenolic compound in a reaction vessel with a volume of 2 liters capable of heating and cooling, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. And 250.00 g of bisphenol F (hydroxyl equivalent: 100) as well as 166.67 g of toluene and 83.33 g of cyclohexanone as organic solvents were added and heated to 100 ° C. to dissolve uniformly. Thereafter, the mixture was cooled to about 35 ° C., and 41.67 g of a 36 wt% formalin solution as an aldehyde and 232.50 g of aniline as a primary amine compound were successively added dropwise. After the addition, the temperature was raised to 80 ° C. for 7 hours. Reaction was performed. Thereafter, this reaction product was taken out, dried under reduced pressure at 130 ° C. for 4 hours, and pulverized to obtain a thermosetting benzoxazine resin (2-2).
Formation of the dihydrobenzoxazine ring was confirmed by absorption at 900 to 1000 cm ⁻¹ by performing FT-IR measurement.
The obtained thermosetting benzoxazine resin (2-2) was formed in the same manner as in Example 1 to form a cured product, which was subjected to the same characteristic test as in Example 1. The results are shown in Table 2.

  As is apparent from Table 1, Examples 1 to 6 of the present invention have toughness in addition to good flexibility due to improvement in bending strength and bending fracture strain rate and reduction in bending elastic modulus. Excellent in heat resistance and adhesiveness with copper foil.

  On the other hand, in the comparative example manufactured without adding a bifunctional epoxy compound and a reaction catalyst, the thermosetting benzoxazine resin of the present invention is not manufactured. Furthermore, as is clear from Table 2, the thermosetting benzoxazine resins of Comparative Examples 1 and 2 are inferior in flexural strength and bending fracture strain, and inferior in flexibility and toughness. Moreover, it is inferior to heat resistance and adhesiveness with copper foil.

Examples 7-12
Using the thermosetting benzoxazine resins (1-1) to (1-6) obtained in Examples 1 to 6, 100 parts by weight of thermosetting benzoxazine resin and 100 parts by weight of phenol novolac type epoxy resin, respectively. Then, 20 parts by weight of melamine-modified phenol resin and 73 parts by weight of methyl ethyl ketone were mixed to prepare thermosetting benzoxazine resin compositions (1-7) to (1-12).
The obtained thermosetting benzoxazine resin compositions (1-7) to (1-12) were each filled into a mold having an internal volume of 100 × 100 × 1 mm, and 180 ° C. for 1 hour with a hydraulic press device. A plate-like molded product was obtained by heating and pressing under the condition of -1.5 MPa. This was cut appropriately and subjected to the bending test and (3). Also, 18 μm electrolytic copper foils were placed one above the other and heated and pressed in the same manner to produce a copper-clad molded article, which was subjected to the solder heat resistance test.
As a result, the thermosetting benzoxazine resin compositions (1-7) to (1-12) of Examples 7 to 12 were all excellent in flexibility, adhesiveness with copper, and heat resistance.

Examples 13-18
Each of the thermosetting benzoxazine resin compositions 7 to 12 obtained in Examples 7 to 12 was impregnated into a glass cloth (style 2116, E glass) having a thickness of about 100 μm, and then dried at 150 ° C. for 5 minutes. Thus, prepregs 13 to 18 having a resin content of 50% by weight were obtained.
The obtained four prepregs were stacked, and a copper foil having a thickness of 18 μm was stacked on both sides thereof, and pressed under 4.0 Mpa, 180 ° C. for 60 minutes, thereby producing copper-clad laminates 13 to 18.
The obtained copper clad laminate was appropriately cut and subjected to the bending test and the solder heat resistance test. Moreover, in the adhesiveness (peel strength) test, the test was conducted without forming a copper film.
As a result, all of the copper clad laminates 13 to 18 of Examples 13 to 18 were excellent in workability, adhesion to copper, and heat resistance.

  An object of the present invention is to provide a thermosetting resin having toughness in addition to high flexibility and having high reliability as a thermosetting resin, a suitable manufacturing method thereof, and curing the resin. It is in providing the hardened | cured material obtained.

Claims (10)

  Thermosetting benzoxazine resin having a phenoxy moiety in the skeleton.   The thermosetting benzoxazine resin according to claim 1, further comprising a hydroxypropylene moiety in the skeleton. Formula (I):

(I)
(Where
R ¹ and R ² are each independently a hydrocarbon group having 1 to 9 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group;
A is absent or a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group, or a sulfonyl group;
D is the following group:

(D)
Where A is as defined above;
m is 0 or a positive integer)
The thermosetting benzoxazine resin of Claim 1 or 2 containing the at least 1 sort (s) of compound shown by these. General formula (II):

(II)
(Where
R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 9 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group;
E and J are each independently absent or a linear hydrocarbon group having 1 to 5 carbon atoms, an isopropylidene group, an oxygen atom, a carbonyl group, and a sulfonyl group;
G is a group:

(G)
Where E and J are as defined above;
n is 0 or a positive integer)
The thermosetting benzoxazine resin of any one of Claims 1-3 containing the at least 1 sort (s) of compound shown by these. General formula (III):

(III)
(Where
Each E is independently absent or a linear hydrocarbon group having 1 to 5 carbon atoms, isopropylidene group, oxygen atom, carbonyl group, sulfonyl group;
L is a group:

(L)
Wherein J is absent or is a linear hydrocarbon group having 1 to 5 carbon atoms, isopropylidene group, oxygen atom, carbonyl group, sulfonyl group; E is Synonymous with the above;
p is a positive integer)
A polyether having a phenol ring terminal represented by
An aldehyde,
A method for producing a thermosetting benzoxazine resin, comprising reacting at least one primary amine compound. The polyether having the phenol ring represented by the above formula (III) at the end is represented by the general formula (IV):

(IV)
(Where E is as defined above)
A bifunctional phenol compound represented by:
Formula (V):

(V)
(Wherein J is as defined above)
The method for producing a thermosetting benzoxazine resin according to claim 5, wherein the bifunctional epoxy compound is a compound obtained by polyhydroxypropyl etherification reaction. General formula (III):

(III)
(Where
Each E is independently absent or a linear hydrocarbon group having 1 to 5 carbon atoms, isopropylidene group, oxygen atom, carbonyl group, sulfonyl group;
L is a group:

(L)
Wherein J is absent or is a linear hydrocarbon group having 1 to 5 carbon atoms, isopropylidene group, oxygen atom, carbonyl group, sulfonyl group; E is Synonymous with the above;
p is a positive integer)
A polyether having a phenol ring terminal represented by
An aldehyde,
A thermosetting benzoxazine resin produced by reacting with one or more primary amine compounds.   The thermosetting obtained by the thermosetting benzoxazine resin according to any one of claims 1 to 4, the thermosetting benzoxazine resin according to claim 7, or the production method according to claim 5 or 6. Cured product obtained by curing a functional benzoxazine resin.   The thermosetting obtained by the thermosetting benzoxazine resin according to any one of claims 1 to 4, the thermosetting benzoxazine resin according to claim 7, or the production method according to claim 5 or 6. A resin composition comprising a functional benzoxazine resin.   The thermosetting obtained by the thermosetting benzoxazine resin according to any one of claims 1 to 4, the thermosetting benzoxazine resin according to claim 7, or the production method according to claim 5 or 6. A metal-clad laminate obtained by using a functional benzoxazine resin or the resin composition according to claim 9.