WO2022085221A1 - Unsaturated group-containing phosphoric acid ester, thermosetting resin composition containing same, and resin material - Google Patents

Abstract

The present invention addresses the problem of providing a highly heat-resistant thermosetting resin composition able to be used in a high frequency printed circuit board. Provided is a phosphoric acid ester compound having an ethylenically unsaturated bond. This compound can be added as a modifier to a thermosetting resin such as an ethylenically unsaturated bond-containing poly(phenylene ether) resin. Also provided is a thermosetting resin composition that contains this modifier and a thermosetting resin. This thermosetting resin composition has the advantage of exhibiting high heat resistance. Furthermore, it is possible to achieve excellent dielectric properties and high heat resistance, which are required of printed circuit boards for next generation communication standards.

Description

Unsaturated group-containing phosphoric acid ester, thermosetting resin composition containing it, and resin material

The present invention relates to a phosphoric acid ester having a copolymerizable unsaturated bond. The present invention particularly relates to unsaturated group-containing phosphoric acid esters useful as modifiers for printed circuit boards and the like. The present invention also relates to resin compositions that can be used in printed circuit boards that comply with next-generation communication standards, such as 5G or 6G communication standards.

Epoxy resin has been widely used in printed circuit boards. Further, it has been conventionally practiced to add a phosphoric acid ester as a flame retardant to an epoxy resin.

As a flame retardant added to the epoxy resin, for example, Japanese Patent Application Laid-Open No. 5-1079 (Patent Document 1) discloses resorcinol bis (2,6-xylyl) phosphate.

Further, Japanese Patent Application Laid-Open No. 2003-221415 (Patent Document 2) discloses di (substituted phenyl) -2- (meth) acryloyloxyethyl phosphate as an unsaturated group-containing phosphoric acid ester having excellent hydrolysis resistance. ing. This document discloses that the problem of hydrolysis resistance during emulsion polymerization or suspension polymerization is solved by this unsaturated group-containing phosphoric acid ester.

However, the resin composition using these additives has a drawback that the heat resistance is lower than that of the resin composition without the additive. This problem of heat resistance is not solved in the above-mentioned Patent Documents 1 and 2. In recent years, information technology has been dramatically developed, and there is a demand for printed circuit boards compatible with 5G (5th generation) or 6G (6th generation) communication standards known as next-generation communication standards. .. These new substrates are required to have dramatically higher processing speeds, which have not been required in the past. In addition, dramatically higher frequencies are being used. In a substrate corresponding to such a next-generation communication standard, the dielectric characteristics of the substrate, particularly the dielectric loss tangent and the transmission loss, become problems when achieving a high processing speed and when using a high frequency. If the dielectric properties of the substrate are not sufficient, high processing speed cannot be achieved and high frequencies cannot be used. Therefore, the substrate for the next-generation communication standard requires excellent dielectric properties. In particular, low dielectric loss tangent and low transmission loss are required.

The dielectric property of the substrate largely depends on the thermosetting resin composition used for the substrate. In particular, the thermosetting resin and the additives added to the resin have a great influence on the dielectric loss tangent and the transmission loss. Therefore, the thermosetting resin composition used for the substrate corresponding to the next-generation communication standard needs to have excellent dielectric properties that were not required for the thermosetting resin composition for the previous printed circuit board. Will be done. It is known that the dielectric loss in a printed circuit board is proportional to the product of the square root of the relative permittivity and the dielectric loss tangent. In the present specification, the product of the square root of the relative permittivity and the dielectric loss tangent is referred to as "contribution to transmission loss". A low contribution of transmission loss is required as a base material for next-generation communication standards. The need for such excellent dielectric properties was not recognized at all during the technological development of Patent Documents 1 and 2.

In addition, high heat resistance is also required for substrates for next-generation communication standards.

Acrylic-modified polyphenylene ether resin is attracting attention as a resin that can achieve the dielectric properties and heat resistance required for a substrate for such a next-generation communication standard, instead of the conventional epoxy resin.

However, a thermosetting resin composition that can solve the above-mentioned problem of reduced heat resistance has not been known. Further, as described above, a thermosetting resin composition capable of producing a substrate having excellent dielectric properties and high heat resistance required for a substrate for a next-generation communication standard has not been known. In particular, no suitable modifier for addition to a resin having an ethylenically unsaturated bond, such as an acrylic-modified polyphenylene ether resin, has been known. For example, in Patent Document 2 above, it is an object to provide an unsaturated group-containing phosphoric acid ester which is less likely to be hydrolyzed during emulsion polymerization or suspension polymerization, and only solving the problem is disclosed. Was there. Therefore, the problem of achieving excellent dielectric properties and high heat resistance is not recognized in Patent Document 2 and is not assumed at all. Further, the above-mentioned Patent Documents 1 and 2 completely describe what kind of modifier is effective for achieving excellent dielectric properties and high heat resistance when added to an acrylic-modified polyphenylene ether resin. No disclosure or suggestion has been made. Therefore, a thermosetting resin composition capable of producing a high-frequency printed circuit board having excellent dielectric properties and high heat resistance corresponding to the next-generation communication standard has not been known.

JP-A-5-1079 Japanese Patent Application Laid-Open No. 2003-221415

The present invention is a compound that can be used as a modifier for a printed circuit board having excellent dielectric properties and high heat resistance, which is required for a substrate for a next-generation communication standard, and a modification for a printed circuit board. It is an object of the present invention to provide a pledge agent and a thermosetting resin composition.

As a result of diligent research to solve the new problems related to the printed circuit board associated with the next-generation communication standard, the present inventor has found that a phosphate ester compound having a specific structure solves the above problems. The present invention has been completed.

Specifically, according to the present invention, for example, the following is provided.

(Item 1)
A compound represented by the following formula (I):

In formula (I)
m is 2 or 1
R ¹ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a linear or branched alkyl group of C ₁ to C ₄ .
R ² is independently located at any of the 2nd to 6th positions of the benzene ring, is a linear or branched alkyl group of C ₁ to C ₄ , and may be the same as R ¹ . May be different,
R ³ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a hydrogen atom or a linear or branched alkyl group of C ₁ to C ₄ , which is the same as R ¹ . It may be different, it may be the same as R ² , or it may be different.
Of the 2nd to 6th positions of the benzene ring, the two carbons in which ^R1 to R3 do not exist ^each have a hydrogen atom.
When m is 2, R ⁴ is independently a linear or branched alkenyl group of C ₂ to C ₁₂ , or the following formula (II) :.

It is a substituent having the structure of
In formula (II)
R ⁵ is independently a hydrogen atom or a methyl group, respectively.
R ⁶ are independently _C2 - _C4 linear or branched-chain alkylenes.
n is an integer of 1-5, and where m is ₁ , ^R4 is a linear or branched alkenyl group of _C2 to C12, a compound.

(Item 2)
The compound according to Item 1 above.
m is 2 or
A compound in which m is 1 and R ⁴ is a linear or branched alkenyl group of C ₃ to C ₁₂ .

(Item 3)
Item 2. The compound according to Item 1 or 2, wherein R ¹ and R ² are an alkyl group at a 2-position and an alkyl group at a 6-position, and R ³ is a hydrogen atom.

(Item 4)
Item 3. The compound according to Item 3, wherein R ¹ and R ² are a methyl group at the 2-position and a methyl group at the 6-position, and R ³ is a hydrogen atom.

(Item 5)
The compound according to any one of Items 1 to 4 above, wherein R ⁴ is a linear or branched alkenyl group of C ₂ to C ₁₂ in the formula (I).

(Item 6)
Item 6. The compound according to any one of Items 1 to 5 above, wherein R ⁴ is a linear or branched alkenyl group of C ₃ to C ₁₂ .

(Item 7)
In the above formula (I), ^R4 is the following formula (III):

It is an alkenyl group having the structure of
Here, in the above equation (III), k is an integer of 0 or more and 10 or less.
Item 5. The compound according to Item 5 or 6.

(Item 8)
Item 2. The compound according to Item 7, wherein k is an integer of 1 or more and 10 or less.

(Item 9)
Item 2. The compound according to Item 7 or 8, wherein m is 1.

(Item 10)
A modifier containing the compound according to any one of the above items 1 to 9.

(Item 11)
A modifier for use in thermosetting resin compositions.
The modifier comprises a compound represented by the following formula (I):

In formula (I)
m is 2 or 1
R ¹ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a linear or branched alkyl group of C ₁ to C ₄ .
R ² is independently located at any of the 2nd to 6th positions of the benzene ring, is a linear or branched alkyl group of C ₁ to C ₄ , and may be the same as R ¹ . May be different,
R ³ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a hydrogen atom or a linear or branched alkyl group of C ₁ to C ₈ , which is the same as R ¹ . It may be different, it may be the same as R ² , or it may be different.
Of the 2nd to 6th positions of the benzene ring, the two carbons in which ^R1 to R3 do not exist ^each have a hydrogen atom.
R ⁴ is independently a linear or branched alkenyl group of C ₂ to C ₁₂ , or R ⁴ is independently of the following formula (II) :.

It is a substituent having the structure of
In formula (II)
R ⁵ is independently a hydrogen atom or a methyl group, respectively.
R ⁶ are independently _C2 - _C4 linear or branched-chain alkylenes.
n is an integer from 1 to 5.
Modifier.

(Item 12)
A thermosetting resin composition comprising the compound according to any one of Items 1 to 9 or the modifier according to Item 10 or 11 and a thermosetting resin.

(Item 13)
Item 12. The thermosetting resin composition according to Item 12, wherein the thermosetting resin contains a thermosetting resin having an ethylenically unsaturated bond.

(Item 14)
Item 12. The thermosetting resin composition according to Item 12 or 13, wherein the thermosetting resin contains a polyphenylene ether resin modified with an ethylenically unsaturated group.

(Item 15)
The thermosetting resin composition according to any one of Items 12 to 14, further comprising a cross-linking agent having an ethylenically unsaturated bond.

(Item 16)
Item 12. The thermosetting resin composition according to Item 15, wherein the cross-linking agent is triallyl isocyanurate.

(Item 17)
The thermosetting resin composition according to any one of Items 12 to 16 above, for producing an insulating layer in a high-frequency printing circuit board.

(Item 18)
A resin material obtained by curing the thermosetting resin composition according to any one of Items 12 to 17 above.

(Item 19)
A high-frequency printed circuit board including a conductor layer and an insulating layer, wherein the insulating layer contains the resin material according to Item 18.

(Item 20)
A method for manufacturing a high-frequency printed circuit board including a conductor layer and an insulating layer, comprising a step of curing the thermosetting resin composition according to Item 17 above to form the insulating layer.

According to the present invention, there are provided a compound that can be used as a modifier for a printed circuit board having excellent heat resistance, a modifier for a printed circuit board, and a thermosetting resin composition. Further, according to the present invention, a compound and a printed circuit board that can be used as a modifier for a printed circuit board having excellent dielectric properties and high heat resistance, which are required for a substrate for a next-generation communication standard. A modifier and a thermosetting resin composition for are provided.

According to the present invention, a phosphoric acid ester compound having an ethylenically unsaturated bond is provided. The details will be described below.

<Compound>
The compound of the present invention is represented by the following general formula (I).

In formula (I), m is 2 or 1. That is, this compound has two ^R4 groups and one phenyl group, or has one ^R4 group and two phenyl groups.

Of the five carbons at positions 2 to 6 of the benzene ring, ^three carbons have ^R1 to R3, and the remaining two carbons each have a hydrogen atom.

R ¹ is independently located at any of the 2nd to 6th positions of the benzene ring, preferably at the 2nd, 3rd, 5th or 6th position of the benzene ring, and more preferably. It is located at either the 2-position or the 6-position of the benzene ring.

R ² is independently located at any of the 2nd to 6th positions of the benzene ring in which R ¹ does not exist, preferably at the 2nd, 3rd, 5th or 6th positions of the benzene ring. It is located at one of the positions, more preferably at either the 2-position or the 6-position of the benzene ring.

In one preferred embodiment, both R ¹ and R ² are located at either the 2-position, 3-position, 5-position or 6-position of the benzene ring, and in a more preferred embodiment, R ¹ and R ² Is located at the 2nd and 6th positions of the benzene ring. In one preferred embodiment, R ¹ and R ² are identical.

R ¹ is an independent linear or branched alkyl group of C ₁ to C ₈ , and in one embodiment, a linear or branched alkyl group of C ₁ to C ₄ . In one embodiment, R ¹ is an alkyl group from C ₁ to C ₂ . In one embodiment, R ¹ is methyl.

In addition, in this specification, "alkyl" means a monovalent group generated by the loss of one hydrogen atom from a saturated aliphatic hydrocarbon (alkane). "Alkylene" refers to a divalent group produced by the loss of one more hydrogen atom from an alkyl. Further, as used herein, the term "alkenyl" refers to a structure in which one of the single bonds in alkyl has a double bond. That is, the alkenyl has one double bond. In the description of each substituent in the present specification, when the alkyl group, the alkylene group or the alkenyl group is a branched chain, the number of carbon atoms thereof is 3 or more. For example, "a linear or branched alkyl group of C ₁ to C ₄ " means "a linear alkyl group of C ₁ to C ₄ or an alkyl group of a branched chain of C ₃ to C ₄ ". Further, for example, "a linear or branched alkenyl group of C ₂ to C ₁₂ " means "a linear alkenyl group of C ₂ to C ₁₂ or an alkenyl group of a branched chain of C ₃ to C ₁₂ ". ..

R ² is an independently linear or branched alkyl group of C ₁ to C ₄ , and in one embodiment, an alkyl group of C ₁ to C ₂ . In one embodiment, R ² is methyl. R ² may be the same as or different from R ¹ .

R ³ is independently located in one of the three carbons in which R ¹ and R ² are absent among the five carbons at positions 2 to 6 of the benzene ring. R ³ is a hydrogen atom or a straight or branched chain alkyl group from C ₁ to C ₈ and, in one embodiment, a hydrogen atom or a straight or branched alkyl group from C ₁ to C ₄ . In one embodiment, R ³ is a hydrogen or an alkyl group from C ₁ to C ₂ . In one embodiment, R ³ is hydrogen or methyl. In one embodiment, R ³ is hydrogen. When R ³ is a hydrogen atom, an alkyl group is present only in two of the five carbons at positions 2 to 6 of the benzene ring, and hydrogen is present in the remaining three carbons. It becomes.

Each of ^R4 is independently a linear or branched _alkenyl group of _C2 to C12, or the following formula (II):

It is a substituent having the structure of. In one preferred embodiment, R ⁴ is a linear or branched chain alkenyl group of C ₂ to C ₁₂ . In one more preferred embodiment, R ⁴ is a linear or branched chain alkenyl group of C ₃ to C ₁₂ . In the most preferred embodiment, ^R4 is an allyl group. In one embodiment, R ⁴ may be a straight chain or branched chain alkenyl group of C ₂ to C ₁₀ , a straight chain or branched chain alkenyl group of C ₂ to C ₈ , C. It may be a linear or branched alkenyl group of ₂ to C6, or it may be a linear or branched _alkenyl group of _C2 to _C4 . Further, in one embodiment, R ⁴ may be a linear or branched alkenyl group of C ₃ to C ₁₀ or a linear or branched alkenyl group of C ₃ to C ₈ . , C ₃ to C ₆ may be a linear or branched alkenyl group, or may be a C ₃ to C ₄ linear or branched alkenyl group.

In one embodiment, R ⁴ is a substituent of formula (II) only if m is 2.

R ⁵ is independently a hydrogen atom or a methyl group.

R ⁶ are independently C ₂ to C ₄ linear or branched chain alkylenes and, in one embodiment, C ₂ alkylene (-CH ₂ CH _2- ).

N is an integer of 1 to 5, and in one embodiment, it is 1.

In one embodiment, ^R4 has the following equation (III):

It is a substituent having the structure of, where k is an integer of 0 or more and 10 or less. In one more preferred embodiment, k is an integer greater than or equal to 1 and less than or equal to 10. In one most preferred embodiment, k is 1. In one embodiment, k may be 1 or more. Further, in one embodiment, k may be 8 or less, 6 or less, 4 or less, or 2 or less.

In a preferred embodiment of the present invention, m is 1 and ^R4 is a substituent having the structure of the formula (III). In a more preferred embodiment, k in formula (III) is 1. In a particularly preferred embodiment, m is 1, R ⁴ is a substituent having the structure of formula (III), k is 1, and R ¹ and R ² are 2-position methyl groups and 6 It is a methyl group at the position ^, and R3 is a hydrogen atom. When a compound in which m is 1 and R ⁴ is a substituent having a structure of the formula (III) is used as a modifier, a composition excellent in both heat resistance and dielectric properties can be obtained. ..

In one embodiment of the invention, if m is 1, R ¹ and R ² are the methyl group at the 2-position and the methyl group at the 6-position, and R ³ is a hydrogen atom, then R ⁴ is not a vinyl group.

<Compound synthesis method>
The compound represented by the formula (I) can be produced by appropriately combining conventionally known processes as a method for synthesizing a phosphoric acid ester.

In formula (I), the compound with m = 1 and ^R4 being alkenyl can be obtained, for example, by reacting the corresponding alkyl substituted phenol with phosphorus oxychloride and an alkenyl alcohol. Specifically, for example, the corresponding alkyl-substituted phenol is reacted with phosphorus oxychloride to synthesize a di (alkyl-substituted phenyl) phosphorochloridate, and then the obtained di (alkyl-substituted phenyl) phosphorochloridate is obtained. Obtained by reacting with alkenyl alcohol.

In formula (I), the compound having m = 2 and ^R4 being alkenyl is, for example, reacting the corresponding alkyl substituted phenol with phosphorus oxychloride to synthesize a mono (alkyl substituted phenyl) phosphorodichloridate. Then, it is obtained by reacting the obtained mono (substituted phenyl) phosphorodichloridate with alkenylphenol.

For example, a compound having m = 1 in formula (I) and ^R4 being a substituent of formula (II) can be produced by the method described in JP-A-2003-221415.

Further, the compound in formula (I) where m = 2 and ^R4 is a substituent of formula (II) can be produced by applying the method described in JP-A-2003-221415. ..
Specifically, for example, a mono (alkyl-substituted phenyl) phosphorodichloridate is synthesized by reacting the corresponding alkyl-substituted phenol with phosphorus oxychloride, and then a hydroxyl group is added to the obtained mono (substituted phenyl) phosphorodichloridate. It is obtained by reacting with a (meth) acrylate containing.

The above compound can be used as it is as a modifier in the present invention.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention contains a thermosetting resin and the above-mentioned modifier.

<Thermosetting resin>
A conventionally known thermosetting resin can be used for the thermosetting resin composition of the present invention. In one preferred embodiment, a thermosetting resin having an ethylenically unsaturated bond is used.

In the present specification, the ethylenically unsaturated bond means an aliphatic double bond or triple bond capable of performing radical polymerization in the presence of radicals. As the group having such an unsaturated bond, various substituents such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group and a maleimide group are well known. The resin obtained by binding these unsaturated bonds to the resin is a thermosetting resin having an ethylenically unsaturated bond, and can be suitably used for the present invention.

As the thermosetting resin having an ethylenically unsaturated bond, conventionally known ones can be used. For example, a polyphenylene ether resin modified with an ethylenically unsaturated group, a maleimide resin, a styrene resin, or the like can be used.

<Polyphenylene ether resin modified with ethylenically unsaturated group>
In one embodiment, the thermosetting resin is a polyphenylene ether resin modified with an ethylenically unsaturated group. The polyphenylene ether resin modified with an ethylenically unsaturated group is a resin in which an ethylenically unsaturated group is bonded to the end of the polyphenylene ether resin.

The polyphenylene ether resin modified with an ethylenically unsaturated group is represented by, for example, the following general formula A.

(General formula A)

In the general formula A, an ethylenically unsaturated group is bonded to the hydrogen atom portion of the hydroxyl group at both ends of the main chain of the polyphenylene ether. Here, in the formula A, R ¹¹ to R ³² are independent hydrogen atoms or substituents, respectively. Examples of the substituent include a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, and a linear or branched group having 2 to 8 carbon atoms. Examples thereof include a chain alkynyl group, an aryl group having 6 to 10 carbon atoms, a carboxyl group, an aldehyde group, a hydroxyl group and an amino group. X, Y, and Z are independently single-bonded, carbonyl group (> C = O), thiocarbonyl group (> C = S), methylene group ( _-CH2- ), ethylene group (dimethylene group) ( -CH ₂ -CH _2- ), isopropenyl group (-C (CH ₃ ) _2- ), trimethylene group (-CH ₂ -CH ₂ -CH _2- ) or tetramethylene group (-CH ₂ -CH ₂ -CH ₂ -CH _2- ), etc. n ¹ is preferably 1 to 100, more preferably 3 to 20. n ² is preferably 1 to 100, more preferably 3 to 20.

In one embodiment, R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁶ , and R ²⁷ are hydrogen. In one embodiment, R ¹⁴ , R ¹⁵ , R ¹⁸ , R ¹⁹ , R ²⁴ , R ²⁵ , R ²⁸ , and R ²⁹ are alkyl, and in one embodiment R ¹⁴ , R ¹⁵ , R ¹⁸ , ,. R ¹⁹ , R ²⁴ , R ²⁵ , R ²⁸ , and R ²⁹ are methyl.

In one embodiment, X and Z are carbonyl groups (> C = O) and Y is an isopropenyl group (-C (CH ₃ ) _2- ). Further, in one embodiment, X is a benzylene group (-C ₆ H ₄ CH _2- ), Y is an isopropenyl group (-C (CH ₃ ) _2- ), and Z is a benzylene group (-CH ₂ C). ₆ H _4- ).

In one embodiment, R ¹³ and R ³² are methyl. In one embodiment, R ¹³ and R ³² are hydrogen.

In one embodiment, R ¹¹ , R ¹² , R ³⁰ and R ³¹ are hydrogen.

The molecular weight of the polyphenylene ether resin modified with an ethylenically unsaturated group is not particularly limited. For example, a number average molecular weight of 500 or more is preferable, and 1,000 or more is more preferable. Further, for example, the number average molecular weight is preferably 10,000 or less, more preferably 7,000 or less, and 5,000 or less in one embodiment. In one embodiment, it is 3,000 or less. If the molecular weight is too small, the Tg of the cured product tends to be low, and the heat resistance tends to be low. If the molecular weight is too large, it may be difficult to mold the cured product because the fluidity is lowered.

Specific preferable resins include, for example, those having the following structures.

As a specific product of the resin having such a structure, for example, SABIC Japan GK Noryl (registered trademark) SA9000 resin is commercially available.
Further, those having the following structures can also be used as preferable resins.

As a specific product of the resin having such a structure, for example, MEGTRON (registered trademark) manufactured by Panasonic Corporation is commercially available.
Further, in one embodiment, the polyphenylene ethers described in JP-A-2003-515642, JP-A-2006-516297, JP-A-2013-23517, JP-A-2013-23519, WO2014 / 0344103, JP-A-2019-194312, etc. are also available. It can be used in the present invention as a thermosetting resin.

<Maleimide resin>
In one embodiment, a maleimide resin can also be used as the thermosetting resin. Any known maleimide resin can be used. Specifically, for example, 4,4'-bismaleimide diphenylmethane, N, N'-p-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, bisphenol. A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, N, N '-(Sulfonyldi-p-phenylene) dimaleimide can be mentioned.

<Styrene resin>
In one embodiment, as the thermosetting resin, a corresponding styrene-based resin in which an allyl group is bonded to a polystyrene side chain can also be used. For example, a polymer having a structural unit represented by the following formula in the molecule is known and can be used in the present invention.

Here, Z ^a indicates an arylene group, R ^1a to R ^3a independently indicate a hydrogen atom or an alkyl group, and R ^4a to R ^6a independently indicate a hydrogen atom or 1 carbon atom. It shows up to 6 alkyl groups. Specific examples of such styrene-based resins include ODV-XET (X03) manufactured by Nittetsu Chemical & Materials Co., Ltd., ODV-XET (X04) manufactured by Nittetsu Chemical & Materials Co., Ltd., and Nittetsu Chemical & Materials Co., Ltd. ODV-XET (X05) manufactured by the company and the like can be mentioned.

<Other resins>
In the thermosetting resin composition of the present invention, if necessary, a thermosetting resin having no ethylenically unsaturated bond is used in addition to the above-mentioned thermosetting resin having an ethylenically unsaturated bond. You can also.

For example, epoxy resin can be used. However, in order to fully exert the effect of the present invention, it is preferable to use a small amount of the thermosetting resin having no ethylenically unsaturated bond. The amount of the thermosetting resin having no ethylenically unsaturated bond is preferably 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond. It is more preferably 10 parts by mass or less.

In the thermosetting resin composition of the present invention, a thermoplastic resin can be used in addition to the thermosetting resin, if necessary. However, in order to fully exert the effect of the present invention, it is preferable to use a small amount of the thermoplastic resin. The amount of the thermoplastic resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and 10 parts by mass or less with respect to 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond. It is more preferable to do so. In one embodiment, the thermosetting resin composition of the present invention does not contain a thermoplastic resin.

<Crosslinking agent>
The thermosetting resin composition of the present invention contains, if necessary, a monomer compound having an ethylenically unsaturated bond as a cross-linking agent. The cross-linking agent having an ethylenically unsaturated bond is copolymerized with a thermosetting resin having an ethylenically unsaturated bond during a thermosetting reaction to provide good physical properties to the obtained cured product.

As the cross-linking agent, a monomer known as a cross-linking agent for a thermosetting resin having an ethylenically unsaturated bond can be used. For example, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, styrene and the like can be used. A monomer having two or more ethylenically unsaturated bonds in one molecule is preferable, and a monomer having three or more ethylenically unsaturated bonds in one molecule is more preferable. Further, a monomer having 4 or less ethylenically unsaturated bonds in one molecule is preferable. In one embodiment, the cross-linking agent is a monomer having three ethylenically unsaturated bonds in the molecule.

Examples of the portion having an ethylenically unsaturated bond in the cross-linking agent include an allyl group, an acryloyl group, and a methacryloyl group. Allyl groups are preferred. The molecular weight of the cross-linking agent is preferably 100 or more, more preferably 200 or more. The molecular weight of the cross-linking agent is preferably 700 or less, more preferably 500 or less, and even more preferably 300 or less.

The amount of the cross-linking agent used is not particularly limited. The amount of the cross-linking agent used is preferably 1 part by mass or more, preferably 3 parts by mass or more, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. It is more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more. If necessary, the amount may be 20 parts by mass or more, or 30 parts by mass or more, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond.

The amount of the cross-linking agent used is preferably 200 parts by mass or less, preferably 150 parts by mass or less, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. It is more preferably 100 parts by mass or less, and further preferably 100 parts by mass or less. If necessary, the amount may be 120 parts by mass or less with respect to 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond, or 100 parts by mass or less.

If the amount of the cross-linking agent used is too small, it may be difficult to obtain sufficient heat resistance in the cured product obtained by curing the thermosetting resin composition. If the amount of the cross-linking agent used is too large, sufficient tensile strength and impact strength may not be obtained in the cured product obtained by curing the thermosetting resin composition.

The modifier compound having an ethylenically unsaturated bond can also function as a cross-linking agent, but in the present invention, the modifier compound having an ethylenically unsaturated bond exerts a remarkable effect as a modifier. Is. Therefore, in the present specification, the modifier compound having an ethylenically unsaturated bond is not included in the cross-linking agent.

<Radical generator>
The thermosetting resin composition of the present invention contains a radical generator, if necessary. The radical generator may be one that generates radicals by heating, or may be one that generates radicals by irradiation with light (for example, visible light or ultraviolet rays).

As the radical generator, any compound known as a radical polymerization initiator of a compound having an ethylenically unsaturated bond can be used. For example, a peroxide-based initiator, an azo-based initiator, or the like can be used.

The amount of the radical generator used is preferably 0.01 part by mass or more, preferably 0.05 part by mass with respect to 100 parts by mass of the total amount of the compounds having an ethylenically unsaturated bond in the thermosetting resin composition. The above is more preferable, 0.1 part by mass or more is further preferable, and 0.5 part by mass or more is particularly preferable. The amount of the radical generator used is preferably 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the compounds having ethylenically unsaturated bonds in the thermosetting resin composition. Is more preferable, and it is further preferable that the content is 3 parts by mass or less. If the amount of the radical generator used is too small, it tends to be difficult to sufficiently cure the thermosetting resin composition. If the amount of the radical generator used is too large, the physical properties of the cured product obtained by curing the thermosetting resin composition as a resin material may not be sufficient.

<Modifier>
In the thermosetting resin composition of the present invention, the above-mentioned phosphoric acid ester compound having an ethylenically unsaturated bond is used as a modifier. As used herein, modifying means improving the properties of the resin, and modifying agent means a compound added to the resin to improve the properties of the resin. The modifier of the present invention is effective for improving the properties of a thermosetting resin, and is particularly effective for improving the properties of a thermosetting resin having an ethylenically unsaturated bond. In one embodiment, the modifier of the present invention can improve the dielectric properties of thermosetting resin compositions. The modifier of the present invention is effective in improving either the dielectric loss tangent or the transmission loss of the thermosetting resin composition, and is also effective in improving both the dielectric loss tangent and the transmission loss. Therefore, the modifier of the present invention can be suitably used for a thermosetting resin composition for a printed circuit board. In particular, it can be preferably used for high-frequency printed circuit boards. In addition, the modifier of the present invention can maintain high heat resistance of the thermosetting resin composition.

The amount of modifier used is not particularly limited. The amount of the modifier used is preferably 1 part by mass or more, preferably 3 parts by mass or more, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. It is more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more. If necessary, the amount may be 20 parts by mass or more, or 30 parts by mass or more, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond.

The amount of the modifier used is preferably 50 parts by mass or less, preferably 40 parts by mass or less, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. Is more preferable, and it is further preferable that the content is 30 parts by mass or less. If necessary, the amount may be 20 parts by mass or less, or 10 parts by mass or less, based on 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond. If the amount of the modifier used is too small, or if the amount of the modifier used is too large, sufficient physical properties may not be obtained in the cured product obtained by curing the thermosetting resin composition. be.

<Reinforcing material>
A reinforcing material can be used in the thermosetting resin composition of the present invention, if necessary.

As the reinforcing material, any known reinforcing material for the thermosetting resin can be used. For example, a fibrous reinforcing material conventionally used as a reinforcing material for an epoxy resin can be used. Specifically, for example, glass fiber or the like can be used.

The reinforcing material may be one that can be uniformly mixed in the thermosetting resin composition, or may be one that cannot be mixed. Examples of the reinforcing material that can be uniformly mixed in the thermosetting resin composition include short fibers of glass, and examples of the reinforcing material that cannot be uniformly mixed in the thermosetting resin composition include glass length. Examples include fibers.

For example, a glass fiber in the shape of a sheet or a mat can be impregnated with a thermosetting resin composition and used as a molding material in the form of a so-called prepreg.

The amount of reinforcing material used is not particularly limited. Specifically, for example, in the thermosetting resin composition, the amount of the reinforcing material is 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin, the cross-linking agent, the radical generator and the modifier. It can be at least parts by mass, at least 30 parts by mass, or at least 50 parts by mass. Further, the amount of the reinforcing material is 300 parts by mass or less, 200 parts by mass or less, based on 100 parts by mass of the total amount of the thermosetting resin, the cross-linking agent, the radical generator and the modifier in the thermosetting resin composition. It can be 150 parts by mass or less, or 100 parts by mass or less.

<Other additives>
The thermosetting resin composition of the present invention includes various types other than the above-mentioned modifiers and reinforcing materials, depending on the properties desired for the resin composition, as long as the effects of the present invention are not affected. Additives can be added. For example, known flame retardants, flame retardants, UV absorbers, antioxidants, light stabilizers, colorants (eg dyes or pigments), surface modifiers, antibacterial agents, insect repellents, antistatic agents, fillings. Agents (eg, inorganic fillers) and the like can be added.

The types and amounts of these additives are not particularly limited, and normally used additives can be used within the range of normal usage amounts. Specifically, for example, each of these additives can be 0.01 part by mass or more with respect to 100 parts by mass of the thermosetting resin, and is 0.1 part by mass or more or 1 part by mass or more. It is also possible, and it is possible to make it 20 parts by mass or less, and it is also possible to make it 10 parts by mass or less or 5 parts by mass or less.

However, the above-mentioned additives such as colorants, ultraviolet absorbers, hydrolysis inhibitors, fillers and the like are not always necessary for the thermosetting resin composition of the present invention. It is sufficient to use these additives in the thermosetting resin composition in the minimum amount necessary based on the performance required for the product manufactured from the thermosetting resin of interest.

<Preparation method of composition>
The mixing and stirring operations in the preparation of the thermosetting resin composition can be performed using a conventional stirring device, for example, various mills, a Henschel mixer (FM mixer), or the like. As long as various components can be mixed uniformly, the order of addition does not matter. All components may be placed in a stirrer at once for mixing and stirring. For example, it is also possible to adopt a procedure in which a material other than the radical generator is mixed first and then the radical generator is mixed.

<Thermosetting reaction>
In the thermosetting resin composition of the present invention, a curing reaction can be carried out by a conventionally known method. For example, if a radical generator is heated or irradiated with light to generate a radical, the generated radical causes a polymerization reaction of the ethylenically unsaturated bond of the thermosetting resin to obtain a cured resin. Be done. Further, if the thermosetting resin composition contains a cross-linking agent, the ethylenically unsaturated bond of the thermosetting resin and the ethylenically unsaturated bond of the cross-linking agent cause a polymerization reaction to obtain a cured resin. .. Further, since the compound and the modifier of the present invention also have an ethylenically unsaturated group, a polymerization reaction of the compound and the modifier of the present invention occurs due to radicals.

The conditions for curing the thermosetting resin composition are appropriately selected according to the type and amount of the radical generator used. For example, if a radical generator that decomposes relatively quickly even at room temperature to generate radicals is used, it may be at room temperature. When using a radical generator that cannot be rapidly decomposed unless it is at a high temperature, a high temperature is used. Specifically, the temperature at which the thermosetting resin composition is cured can be, for example, 80 ° C. or higher, 100 ° C. or higher, and for example, 250 ° C. or lower, or 230 ° C. or lower. can. The heating time can be, for example, 1 minute or more or 3 minutes or more, and can be, for example, 120 minutes or less or 90 minutes or less.

When a curing reaction is carried out in the thermosetting resin composition of the present invention, a copolymer containing residues of a thermosetting resin having an ethylenically unsaturated bond and residues of a compound of the present invention or a modifier of the present invention is contained. Is considered to be formed. Further, when the thermosetting resin composition of the present invention is subjected to a curing reaction by including a cross-linking agent, the residue of the thermosetting resin having an ethylenically unsaturated bond and the compound of the present invention or the modifier of the present invention are used. It is believed that a copolymer containing the residues of the cross-linking agent and the residues of the cross-linking agent is formed. It is understood that the substrate produced by using the thermosetting resin composition of the present invention has excellent dielectric properties and heat resistance due to the excellent dielectric properties and heat resistance of the copolymer thus formed. The cured product obtained by performing a curing reaction in the thermosetting resin composition of the present invention has excellent dielectric properties and heat resistance, and can be preferably used as a material for producing a printed circuit board. In addition, in this specification, a "resin material" is a cured product obtained by performing a curing reaction in a thermosetting resin composition, and refers to a material that can be used for various purposes.
In the chemical structure of the resin in the cured product, a radical polymerization reaction occurs at a portion of the ethylenically unsaturated bond in the molecule of each component in the thermosetting resin composition, resulting in a structure in which a plurality of molecules are bonded. However, it is difficult to specify the chemical structure exactly. In particular, when there are multiple types of molecules with ethylenically unsaturated bonds, there is a possibility that homopolymerization and copolymerization will occur, so the chemical structure of the product should be strictly specified. Is difficult, and even if it is theoretically possible, it requires a lot of money and time, which is not practical. Therefore, the composition of the thermosetting resin composition before the curing reaction is specified, and the cured product is described as a cured product obtained by curing the composition by the expression of so-called product-by-process.

<Molded product>
The thermosetting resin composition of the present invention can be molded by any method known as a method for molding a thermosetting resin. A desired molded product can be easily obtained by using a molding machine, a mold, or the like corresponding to the desired molded product. For example, it is possible to obtain a desired molded product by performing molding and a curing reaction of a thermosetting resin by a method such as a heat press. The step of performing the curing reaction in the thermosetting resin composition and the step of molding into a desired shape may be performed at the same time or separately. The cured product obtained by performing the curing reaction first may be molded, or the curing reaction may be performed after the molding step is performed first.

The obtained molded product has excellent dielectric properties and has the advantage that the heat resistance is not reduced due to the addition of the modifier.

<Printed circuit board>
By curing the thermosetting resin composition containing the above-mentioned thermosetting resin and modifier, a substrate that can be used as a printed circuit board can be obtained. The printed circuit board usually has a conductor layer and an insulating layer. The modifier and thermosetting resin composition of the present invention can be used to form an insulating layer of a printed circuit board.

In the present specification, the high frequency is not particularly limited, but is preferably 100 MHz or higher, 1 GHz or higher in one embodiment, and 10 GHz or higher in another embodiment. Further, the high frequency may be, for example, 100 GHz or less, or may be 50 GHz or less. In the present specification, the printed circuit board for high frequency means a printed circuit board in which such a high frequency is used.

High-frequency printed circuit boards are required to have high heat resistance. If a substrate is manufactured using the thermosetting resin of the present invention, excellent heat resistance can be achieved. Further, if a substrate is manufactured using the thermosetting resin of the present invention, excellent dielectric properties and heat resistance can be achieved, so that the substrate can be suitably used for a high frequency printed circuit board.

The present invention will be described more specifically by the following examples, but the present invention is not limited to the following examples.

(material)
The following compounds were used as raw materials in the following synthetic examples.
・ Phosphoryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2,6-Dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Allyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Synthesis Example 1A) Synthesis of monoxysilylphosphologi chloride (MXPC) Phosphoryl oxychloride in a 4-necked flask with a capacity of 2 liters equipped with a stirrer, a thermometer and a hydrochloric acid recovery device (a condenser connected with a water scrubber). It was filled with 1500 g, 611 g of 2,6-dimethylphenol and 1.2 g of magnesium chloride as a catalyst.

The obtained mixed solution was gradually heated to a temperature of 110 ° C. over about 3 hours while stirring to react, and the generated hydrogen chloride (hydrochloric acid gas) was recovered with a water scrubber. Then, the pressure in the flask is gradually reduced to 12 kPa at 120 ° C. to remove unreacted phosphorus oxychloride and phenol, and hydrogen chloride produced as a by-product, and the main component is monophenylphosphologi chloride having the following structural formula. 1200 g of the reaction mixture was obtained. The chlorine content of the reaction mixture was 28.3% by mass.

(Synthesis Example 1B) Compound (1)
34.8 g of allyl alcohol, 60.7 g of triethylamine as a hydrogen halide scavenger, and 4-dimethylaminopyridine 7 as a catalyst in a 0.5 liter 4-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser. It was filled with 3 g and 200 g of toluene as a solvent. Further, the dropping funnel was filled with 71.7 g of the monokisilylphosphologi chloride obtained in Synthesis Example 1.

The mixed solution in the four-necked flask was adjusted to a temperature of 20 ° C. with stirring, and the monoxylylphosphologi chloride in the dropping funnel was added dropwise over 1 hour while maintaining the same temperature (20 ° C.). After completion of the dropping, the mixture was stirred at the same temperature for 2 hours to obtain a reaction product. The obtained reaction product was washed with dilute hydrochloric acid and water, neutralized and washed with sodium carbonate and water, heated to a temperature of 50 ° C., reduced to 2 kPa, and water, toluene and low boiling point were distilled off at room temperature. The mixture was cooled to 76.2 g of a yellow liquid.
The results of NMR measurements were as follows.
^{1 1} H-NMR spectrum (400 MHz, CDCl ₃ , δ ppm): 7.00 (3H, m), 5.92 (2H, m), 5.35 (2H, d), 5.23 (2H, d), 4.61 (4H, m), 2.36 (6H, m)
³¹ P-NMR spectrum (400 MHz, CDCl ₃ , δ ppm): -0.1, -5.1, -10.3.
The phosphorus atom content determined according to ASTM D1091 was 10.70%. From the above analysis results, it was confirmed that this product contained 86.7% of the substance having the following structural formula.

(Synthesis Example 2) Compound (2)
Compound (2) was obtained according to the procedure described in JP-A-2003-221415, paragraphs 0050 to 0052.

(Compound (3))
As the compound (3), a commercially available resorcinol bis (2,6-kisilyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX-200) was used.

(Synthesis Example 3 (Compound (4)))
The following formula:

The compound of was synthesized by the following procedure.

(Synthesis Example 4A) Synthesis of Dixysilyl Phosphoryl Chloridet (DXPC) In a 4-necked flask with a capacity of 2 liters equipped with a stirrer, a thermometer and a hydrochloric acid recovery device (a condenser connected with a water scrubber), 767 g of phosphorus oxychloride. , 1200 g of 2,6-dimethylphenol, 140 g of xylene as a solvent, and 6.2 g of magnesium chloride as a catalyst were charged.

The obtained mixed solution was gradually heated to a temperature of 160 ° C. over about 3 hours while stirring to react, and the generated hydrogen chloride (hydrochloric acid gas) was recovered with a water scrubber. Then, at the same temperature, the pressure in the flask was gradually reduced to 20 kPa to remove xylene, unreacted phosphorus oxychloride, 2,6-dimethylphenol, and hydrogen chloride produced as a by-product. 1700 g of a reaction mixture containing lolidate as a main component was obtained. The chlorine content of the reaction mixture was 10.9% by mass.

(Synthesis Example 4B) Compound (4)
In a 4-necked flask with a capacity of 2 liters equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 487.1 g of the dixysilylphosphologic chloride obtained in Synthesis Example A and 151.8 g of triethylamine as a hydrogen halide scavenger. , 18.3 g of 4-dimethylaminopyridine as a catalyst and 500 g of toluene as a solvent. Further, the dropping funnel was filled with 87.1 g of allyl alcohol.

The temperature of the mixed solution in the four-necked flask was adjusted to 20 ° C. while stirring, and the allyl alcohol in the dropping funnel was added dropwise over 1 hour and 30 minutes while maintaining the same temperature (20 ° C.). After completion of the dropping, the mixture was stirred at the same temperature for 8 hours to obtain a reaction product. The obtained reaction product was washed with dilute hydrochloric acid and water, neutralized and washed with sodium carbonate and water, heated to a temperature of 50 ° C., reduced to 2 kPa, and water, toluene and low boiling point were distilled off at room temperature. The mixture was cooled to 508.6 g of a yellow liquid.

The results of NMR measurements were as follows.
^{1 1} H-NMR spectrum (400 MHz, CDCl ₃ , δ ppm): 7.00 (6H, m), 5.78 (1H, m), 5.24 (1H, d), 5.14 (1H, d), 4.61 (2H, m), 2.32 (12H, m)
³¹ P-NMR spectrum (400 MHz, CDCl ₃ , δ ppm): -10.3, -15.8, -24.4

The phosphorus atom content determined according to ASTM D1091 was 8.90%. From the above analysis results, it was confirmed that this product contained 97.2% of the substance having the following structural formula.

<Experiment A>
(Examples 1A and 2A and Comparative Examples 1A and 2A)
The experiments of Example 1A and Example 2A and Comparative Example 1A and Comparative Example 2A were performed as follows.

(Forming of laminated board and evaluation of physical properties)
In the examples, the following compounds were used as raw materials.
-Resin: Methacrylic acid-modified polyphenylene ether resin (SABIC SA-9000, methacrylic acid-modified polyphenylene ether resin at the end, 2 terminal methacryloyl groups)
-Crosslinking agent: Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Radical generator: 1,3-bis (t-butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF CORPORATION)

<Preparation of resin composition and evaluation of physical properties>
A thermosetting resin composition was prepared by blending various components in the ratios shown in Table 1, and 1.3 g of the resin composition was impregnated into 2.0 g of a glass cloth having a texture of 100 g / m ² for 10 minutes at room temperature. , 120 ° C. was dried in an oven for 3 minutes to obtain a prepreg. Next, eight prepregs were stacked, sandwiched between stainless steel mirror plates, and cured at a temperature of 210 ° C. and a press pressure of 3 MPa for 60 minutes using a hot press to obtain a sample of the laminated plate.

(Test method)
Glass transition temperature: According to JIS K 7244, Hitachi High-Tech Science Co., Ltd., using a dynamic viscoelasticity measuring device, bending mode, nitrogen atmosphere, measurement frequency 10 Hz, temperature rise rate 5 ° C / min, loss coefficient ( Obtained from tan δ).

It was confirmed that the glass transition temperature in Example 1A and Example 2A was higher than that of Comparative Example 2A, and the decrease in the glass transition temperature due to the addition of the modifier was small. From this, it was confirmed that the decrease in heat resistance due to the addition of the modifier was small.

<Experiment B>
The experiments of Example 1B, Example 2B and Example 3, and Comparative Example 1B and Comparative Example 2B were carried out in a facility different from the facility where Experiment A was performed as follows.

(Examples 1B and 2B and Comparative Examples 1B and 2B)
The same experiments as in Examples 1B and 2A and Comparative Examples 1A and 2A were performed again. The results are shown in Table 2 below.

It was confirmed that the glass transition temperature in Example 1B and Example 2B was higher than that of Comparative Example 2B, and the decrease in the glass transition temperature due to the addition of the modifier was small. From this, it was confirmed that the decrease in heat resistance due to the addition of the modifier was small.

(Example 3 and Comparative Examples 1B to 2B)
(Forming of laminated board and evaluation of physical properties)
In Example 3, the following compounds were used as raw materials.
-Resin: Methacrylic acid-modified polyphenylene ether resin (SABIC SA-9000, methacrylic acid-modified polyphenylene ether resin at the end, 2 terminal methacryloyl groups)
-Crosslinking agent: Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Radical generator: 1,3-bis (t-butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF CORPORATION)

<Preparation of resin composition and evaluation of physical properties>
In Example 3, a thermosetting resin composition was prepared by blending various components in the ratio shown in Table 3, and a sample of a laminated board was obtained by the same method as in Comparative Examples 1A and 2A.

(Test method)
(1) Glass transition temperature: In Example 3, the measurement was carried out by the same method as in Comparative Examples 1A and 2A. The results are shown in Table 3. For Comparative Example 1B and Comparative Example 2B, the measurement results of the glass transition temperature of Comparative Example 1B and Comparative Example 2B shown in Table 2 are shown again in Table 3.
(2) Dielectric loss tangent: In the sample of Example 3 and the samples of Comparative Examples 1B and 2B, the dielectric loss tangent was measured. Specifically, in accordance with IEC62810, a dielectric loss tangent (tanδ) at a frequency of 10 GHz was obtained by the cavity resonator perturbation method using a PNA network analyzer manufactured by Keysight Technology Co., Ltd. and a cavity resonator manufactured by Kanto Electronics Applied Development Co., Ltd. rice field.
In the table, the addition amount is by mass.

(3) Contribution to transmission loss: The contribution to transmission loss was determined in the sample of Example 3 and the sample of Comparative Example 1B. Specifically, when the dielectric loss tangent (tan δ) was measured, the relative permittivity (εr) was further determined. From the obtained dielectric loss tangent (tan δ) value and relative permittivity (εr) value, the contribution of transmission loss was determined based on the following equation (A).

The contribution of transmission loss is an index showing the degree of deterioration of electrical signals in a printed circuit board, and since the square root of the relative permittivity is multiplied by the dielectric loss tangent, this value determines the performance of transmission efficiency due to the composition of the resin. It is a value to reflect. If this value is low, it means that the transmission efficiency of the electric signal is high.

It was confirmed that the glass transition temperature in Example 3 was higher than that of Comparative Example 2B, and the decrease in the glass transition temperature due to the addition of the modifier was small. Further, in Example 3, excellent dielectric properties were confirmed. That is, it was confirmed that the dielectric loss tangent and the contribution of transmission loss were lower than those of Comparative Example 1B, and the dielectric characteristics were excellent. Therefore, it is understood that the transmission efficiency of electric signals is high. From this, it was confirmed that in Example 3, high heat resistance was maintained in the cured product and the decrease in heat resistance due to the addition of the modifier was small.

From the results of Experiment A and Experiment B above, it was confirmed that high heat resistance can be achieved by the modifier of the present invention. Further, from the results of Experiment B, it was confirmed that excellent dielectric properties and high heat resistance can be achieved at the same time by using the modifier of the preferred embodiment.

According to the present invention, a modifier and a thermosetting resin composition for a printed circuit board having excellent heat resistance are provided. INDUSTRIAL APPLICABILITY According to the present invention, a modifier and a thermosetting resin composition particularly suitable for a high-frequency printed circuit board corresponding to a next-generation communication standard are provided. According to the modifier and the thermosetting resin composition of the present invention, a printed circuit board having high electric signal transmission efficiency and excellent heat resistance is provided.

As described above, the present invention has been exemplified using the preferred embodiment of the present invention, but the present invention should not be construed as being limited to this embodiment. It is understood that the invention should be construed only by the claims. It will be understood by those skilled in the art that from the description of a specific preferred embodiment of the present invention, an equivalent range can be implemented based on the description of the present invention and common general technical knowledge. The patents, patent applications and documents cited herein are to be incorporated by reference in their content as they are specifically described herein. Understood.

Claims (20)

1. A compound represented by the following formula (I):
   

   

   In formula (I)
   m is 2 or 1
   R ¹ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a linear or branched alkyl group of C ₁ to C ₄ .
   R ² is independently located at any of the 2nd to 6th positions of the benzene ring, is a linear or branched alkyl group of C ₁ to C ₄ , and may be the same as R ¹ . May be different,
   R ³ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a hydrogen atom or a linear or branched alkyl group of C ₁ to C ₄ , which is the same as R ¹ . It may be different, it may be the same as R ² , or it may be different.
   Of the 2nd to 6th positions of the benzene ring, the two carbons in which ^R1 to R3 do not exist ^each have a hydrogen atom.
   When m is 2, R ⁴ is independently a linear or branched alkenyl group of C ₂ to C ₁₂ , or the following formula (II) :.
   

   

   It is a substituent having the structure of
   In formula (II)
   R ⁵ is independently a hydrogen atom or a methyl group, respectively.
   R ⁶ are independently _C2 - _C4 linear or branched-chain alkylenes.
   n is an integer of 1-5, and where m is ₁ , ^R4 is a linear or branched alkenyl group of _C2 to C12, a compound.
2. The compound according to claim 1.
   m is 2 or
   A compound in which m is 1 and R ⁴ is a linear or branched alkenyl group of C ₃ to C ₁₂ .
3. The compound according to claim 1 or 2, wherein R ¹ and R ² are an alkyl group at a 2-position and an alkyl group at a 6-position, and R ³ is a hydrogen atom.
4. The compound according to claim 3, wherein R ¹ and R ² are a methyl group at the 2-position and a methyl group at the 6-position, and R ³ is a hydrogen atom.
5. The compound according to any one of claims 1 to 4, wherein in the formula (I), R ⁴ is a linear or branched alkenyl group of C ₂ to C ₁₂ .
6. The compound according to any one of claims 1 to 5, wherein R ⁴ is a linear or branched alkenyl group of C ₃ to C ₁₂ .
7. In the above formula (I), ^R4 is the following formula (III):
   

   

   It is an alkenyl group having the structure of
   Here, in the above equation (III), k is an integer of 0 or more and 10 or less.
   The compound according to claim 5 or 6.
8. The compound according to claim 7, wherein k is an integer of 1 or more and 10 or less.
9. The compound according to claim 7 or 8, wherein m is 1.
10. A modifier containing the compound according to any one of claims 1 to 9.
11. A modifier for use in thermosetting resin compositions.
    The modifier comprises a compound represented by the following formula (I):
    

    

    In formula (I)
    m is 2 or 1
    R ¹ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a linear or branched alkyl group of C ₁ to C ₄ .
    R ² is independently located at any of the 2nd to 6th positions of the benzene ring, is a linear or branched alkyl group of C ₁ to C ₄ , and may be the same as R ¹ . May be different,
    R ³ is independently located at any of the 2nd to 6th positions of the benzene ring, and is a hydrogen atom or a linear or branched alkyl group of C ₁ to C ₈ , which is the same as R ¹ . It may be different, it may be the same as R ² , or it may be different.
    Of the 2nd to 6th positions of the benzene ring, the two carbons in which ^R1 to R3 do not exist ^each have a hydrogen atom.
    R ⁴ is independently a linear or branched alkenyl group of C ₂ to C ₁₂ , or R ⁴ is independently of the following formula (II) :.
    

    

    It is a substituent having the structure of
    In formula (II)
    R ⁵ is independently a hydrogen atom or a methyl group, respectively.
    R ⁶ are independently _C2 - _C4 linear or branched-chain alkylenes.
    n is an integer from 1 to 5.
    Modifier.
12. A thermosetting resin composition comprising the compound according to any one of claims 1 to 9, the modifier according to claim 10 or 11, and a thermosetting resin.
13. The thermosetting resin composition according to claim 12, wherein the thermosetting resin contains a thermosetting resin having an ethylenically unsaturated bond.
14. The thermosetting resin composition according to claim 12 or 13, wherein the thermosetting resin contains a polyphenylene ether resin modified with an ethylenically unsaturated group.
15. The thermosetting resin composition according to any one of claims 12 to 14, further comprising a cross-linking agent having an ethylenically unsaturated bond.
16. The thermosetting resin composition according to claim 15, wherein the cross-linking agent is triallyl isocyanurate.
17. The thermosetting resin composition according to any one of claims 12 to 16, for producing an insulating layer in a high-frequency printed circuit board.
18. A resin material obtained by curing the thermosetting resin composition according to any one of claims 12 to 17.
19. A high-frequency printed circuit board including a conductor layer and an insulating layer, wherein the insulating layer contains the resin material according to claim 18.
20. A method for manufacturing a high-frequency printed circuit board including a conductor layer and an insulating layer, comprising a step of curing the thermosetting resin composition according to claim 17 to form the insulating layer.