WO2023210567A1

WO2023210567A1 - Resin composition, cured product, prepreg, metal foil clad laminated plate, resin composite sheet, printed wiring board, semiconductor device, and printed wiring board manufacturing method

Info

Publication number: WO2023210567A1
Application number: PCT/JP2023/016071
Authority: WO
Inventors: 晃樹小松; 佳亮奥村; 智絵森下; 恵東原; 恵一長谷部
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2022-04-27
Filing date: 2023-04-24
Publication date: 2023-11-02
Also published as: TW202400696A

Abstract

Provided are: a resin composition that can, when formed into a cured product, suppress backside exposure; and a cured product, a prepreg, a metal foil clad laminated plate, a resin composite sheet, a printed wiring board, a semiconductor device, and a printed wiring board manufacturing method, all using the resin composition. The resin composition contains a thermosetting compound. A cured product, of the resin composition, molded so as to have a thickness of 30 μm exhibits a transmission rate of 0.070% or less with respect to g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm).

Description

Resin composition, cured product, prepreg, metal foil-clad laminate, resin composite sheet, printed wiring board, semiconductor device, and method for producing printed wiring board

The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, a semiconductor device, and a method for manufacturing a printed wiring board.

In recent years, the integration and miniaturization of semiconductor elements used in mobile terminals, electronic equipment, communication equipment, etc. have been accelerating. Along with this, there is a need for technology that enables high-density packaging of semiconductor elements, and improvements are also needed for printed wiring boards, which play an important role.

Here, mainly as the final step of the printed wiring board processing method, a method is used in which a solder resist is applied to the printed wiring board on which an electronic circuit is formed, and an insulating film is formed to protect the circuit pattern. Several methods are known for forming a coating film using solder resist. For example, in the method using a developable solder resist, solder resist is applied over the entire circuit pattern of a printed wiring board, and a predetermined pattern is formed. The solder resist layer is exposed to light through a negative film (mask) on which a circuit pattern is made, and the uncured portions are developed.

However, when this method is used for a printed wiring board with electronic circuits formed on both sides, the light irradiated on one side passes through the printed wiring board substrate and acts on the solder resist layer on the opposite side. , which may leave resist residue on the opposite side where it is supposed to be removed. This phenomenon in which the light irradiated on one side acts on the solder resist layer on the opposite side is called back exposure.
Here, as a means to solve such back exposure, Patent Document 1 describes a composition for suppressing back exposure of a photosensitive composition that is cured by light with a wavelength of 350 to 420 nm as a composition for an insulating layer. The use of a composition comprising a compound (A) having a naphthalene skeleton and a substituent bonded to at least the 2-position and/or the 7-position of the naphthalene ring contained in the naphthalene skeleton is disclosed. .

International Publication No. 2020/162278

As mentioned above, resin compositions that solve the problem of back exposure are known, but with recent technological innovations, resin layers (insulating layers) for printed wiring boards have become thinner and Exposure problems are becoming more serious. Therefore, there is a need for a resin composition that can provide a resin layer (cured product) that can suppress new back exposure.
The present invention aims to solve such problems, and provides a resin composition that can suppress back exposure when made into a cured product, as well as a cured product and prepreg using the resin composition. The present invention aims to provide a metal foil-clad laminate, a resin composite sheet, a printed wiring board, a semiconductor device, and a method for manufacturing a printed wiring board.

Based on the above-mentioned problems, the present inventor conducted a study and found a resin composition that has low transmittance for all G-line (wavelength: 436 nm), H-line (wavelength: 405 nm), and I-line (wavelength: 365 nm). We have found that the above problems can be solved by doing so.
Specifically, the above problem was solved by the following means.
<1> A resin composition containing a thermosetting compound,
A resin composition in which the transmittance of g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm) in a cured product molded to a thickness of 30 μm is 0.070% or less, respectively. thing.
<2> The resin composition according to <1>, wherein the cured product molded to a thickness of 30 μm has a transmittance of H-line (wavelength 405 nm) of 0.050% or less.
<3> The resin composition according to <1> or <2>, wherein the cured product molded to a thickness of 30 μm has an i-line (wavelength 365 nm) transmittance of 0.040% or less.
<4> The resin composition according to any one of <1> to <3>, containing an ultraviolet absorber and/or a nonmetallic organic dye.
<5> The resin composition according to any one of <1> to <3>, containing an ultraviolet absorber and a nonmetallic organic dye.
<6> The resin composition according to <4> or <5>, wherein the nonmetallic organic dye contains a dye.
<7> Any one of <4> to <6>, wherein the content of the ultraviolet absorber is more than 0 parts by mass and 3.0 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. The resin composition described in .
<8> Any one of <4> to <7>, wherein the content of the nonmetallic organic dye is more than 0 parts by mass and 2.0 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. 1. The resin composition according to item 1.
<9> Any one of <4> to <8>, wherein the mass ratio of the ultraviolet absorber to the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is 0.15 to 4.0. The resin composition described in .
<10> Any one of <4> to <8>, wherein the mass ratio of the ultraviolet absorber to the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is 0.4 to 1.5. The resin composition described in .
<11> The thermosetting compound is a maleimide compound, an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and is represented by formula (V) The resin composition according to any one of <1> to <10>, which contains one or more selected from the group consisting of a polymer having a structural unit and a cyanate ester compound.
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
<12> The resin composition according to any one of <1> to <11>, wherein a dielectric loss tangent of a cured product of the resin composition is 0.0001 or more and less than 0.0027.
<13> The resin composition according to any one of <1> to <12>, further comprising a filler.
<14> The resin composition according to <13>, wherein the content of the filler is 10 to 1000 parts by mass based on 100 parts by mass of resin solids in the resin composition.
<15> The resin composition according to any one of <1> to <14>, which is for forming an insulating layer.
<16> The transmittance of the H-line (wavelength 405 nm) in the cured product molded to a thickness of 30 μm is 0.050% or less,
The transmittance of i-line (wavelength 365 nm) in the cured product molded to a thickness of 30 μm is 0.040% or less,
Contains UV absorbers and non-metallic organic pigments,
the non-metallic organic pigment contains a dye,
The content of the ultraviolet absorber is more than 0 parts by mass and 3.0 parts by mass or less with respect to 100 parts by mass of resin solid content in the resin composition,
The content of the non-metallic organic dye is more than 0 parts by mass and 2.0 parts by mass or less with respect to 100 parts by mass of resin solid content in the resin composition,
The mass ratio of the ultraviolet absorber and the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is 0.4 to 1.5,
The thermosetting compound includes a maleimide compound, an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and a structural unit represented by formula (V). The resin composition according to any one of <1> to <15>, containing one or more selected from the group consisting of a cyanate ester compound and a cyanate ester compound.
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
<17> A cured product of the resin composition according to any one of <1> to <16>.
<18> A prepreg formed from a base material and the resin composition according to any one of <1> to <16>.
<19> A layer formed from the resin composition according to any one of <1> to <16> and/or a layer formed from the prepreg according to <18>, and one side of the layer or A metal foil-clad laminate comprising: metal foil arranged on both sides.
<20> A resin composite sheet comprising a support and a layer formed from the resin composition according to any one of <1> to <16> disposed on the surface of the support.
<21> A printed wiring board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is made of the resin composition according to any one of <1> to <16>. A printed wiring board comprising at least one of a layer formed from a material and a layer formed from a prepreg according to <18>.
<22> The printed wiring board according to <21>, wherein the insulating layer has an insulating layer having a thickness of 15 μm or less.
<23> A semiconductor device including the printed wiring board according to <22>.
<24> At least one insulating layer comprising a cured product of the resin composition according to any one of <1> to <16>;
a step of preparing a substrate laminated with at least one conductor layer in contact with the insulating layer;
forming a photosensitive composition layer that is cured by light with a wavelength of 350 to 440 nm on both sides of the substrate;
arranging a mask pattern on at least one surface of the photosensitive composition layer, and exposing the photosensitive composition layer to light with a wavelength of 350 to 440 nm through the mask pattern,
A method for manufacturing printed wiring boards.
<25> A substrate comprising at least one insulating layer containing a cured product of the resin composition according to any one of <1> to <16> and at least one conductor layer in contact with the insulating layer. forming a photosensitive composition layer on both sides that is cured by light with a wavelength of 350 to 440 nm;
arranging a mask pattern on at least one surface of the photosensitive composition layer, and exposing the photosensitive composition layer to light with a wavelength of 350 to 440 nm through the mask pattern,
A method for manufacturing printed wiring boards.
<26> The method for manufacturing a printed wiring board according to <24> or <25>, wherein the insulating layer has an insulating layer having a thickness of 15 μm or less.

According to the present invention, a resin composition that can suppress back exposure when made into a cured product, as well as a cured product, prepreg, metal foil-clad laminate, resin composite sheet, printed wiring board, using the resin composition, It is now possible to provide semiconductor devices and printed wiring board manufacturing methods.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. Note that the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having no substituent (atomic group) as well as a group having a substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, for expressions that do not indicate substitution or non-substitution, non-substitution is preferred.
In the present specification, the (meth)allyl group represents allyl and/or methallyl, "(meth)acrylate" represents both acrylate and/or methacrylate, and "(meth)acrylate" represents acrylate and/or methacrylate; "Acrylic" represents both or either of acrylic and methacrylic, and "(meth)acryloyl" represents both or either of acryloyl and methacryloyl.
In this specification, the relative dielectric constant refers to the ratio of the dielectric constant to the vacuum dielectric constant of a substance. Further, in this specification, the relative dielectric constant may be simply referred to as "permittivity."
In addition, in this specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
In this specification, various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated.
In this specification, the term "process" is used not only to refer to an independent process, but also to include any process that achieves the intended effect even if it cannot be clearly distinguished from other processes. .
If the measurement methods, etc. explained in the standards shown in this specification differ from year to year, unless otherwise stated, they shall be based on the standards as of January 1, 2022.

In this specification, resin solid content refers to components excluding fillers (fillers such as inorganic fillers and resin fillers) and solvents, including thermosetting compounds, aromatic oligomers, thermoplastic elastomers, and other resins. It is intended to contain additive components (ultraviolet absorbers, non-metallic organic dye additives, etc.).

The resin composition of this embodiment is a resin composition containing a thermosetting compound, and in a cured product molded to a thickness of 30 μm, G-line (wavelength 436 nm), H-line (wavelength 405 nm), and I-line (wavelength: 365 nm) is characterized by a transmittance of 0.070% or less. In this embodiment, when the cured product has a thickness of 30 μm, back exposure can be effectively suppressed by setting the light transmittance of each of the wavelengths to 0.070% or less.
In addition, when a cured product formed from a conventional resin composition is used for an ultra-thin insulating layer of a printed wiring board, circuit patterns in the inner layer may be detected as defects during AOI (Automated Optical Inspection). There is a problem with this. This problem is particularly likely to occur when the insulating layer does not contain a filler (particularly an inorganic filler, furthermore, a glass cloth, a filler, etc.). In the resin composition of this embodiment, such problems can be effectively avoided.

The resin composition of the present embodiment has a transmittance of g-line (wavelength 436 nm) of 0.070% or less, preferably 0.069% or less, in a cured product molded to a thickness of 30 μm. It is more preferably 0.068% or less, even more preferably 0.067% or less, even more preferably 0.066% or less, and even more preferably 0.065% or less. The lower limit of the transmittance of the g-line (wavelength 436 nm) is ideally 0%, but 0.001% or more is practical.

The resin composition of the present embodiment also has a transmittance of H-line (wavelength 405 nm) of 0.070% or less, and 0.050% or less in a cured product molded to a thickness of 30 μm. Preferably, it is 0.045% or less, more preferably 0.040% or less, even more preferably 0.038% or less, even more preferably 0.035% or less. . Ideally, the lower limit of the transmittance of the h-line (wavelength: 405 nm) is 0%, but 0.001% or more is practical.

The resin composition of the present embodiment further has a transmittance of i-line (wavelength 365 nm) of 0.070% or less and 0.040% or less in a cured product molded to a thickness of 30 μm. It is more preferably 0.030% or less, even more preferably 0.025% or less, and even more preferably 0.020% or less. The lower limit of the transmittance of the i-line (wavelength: 365 nm) is ideally 0%, but 0.001% or more is practical.

A means of achieving low light transmittance in the above G-line (wavelength 436 nm), H-line (wavelength 405 nm), and I-line (wavelength 365 nm) is to select the type of thermosetting compound to be added to the resin composition. and other ingredients. However, if the type of thermosetting compound is adjusted or various additives are added to the resin composition in order to suppress back exposure, the cured product of the resin composition may have low dielectric properties (low dielectric constant and/or (low dielectric loss tangent) may decrease. Therefore, in this embodiment, it is preferable to adjust the light transmittance to satisfy the above-mentioned light transmittance by using a resin composition containing an ultraviolet absorber and/or a non-metallic organic dye. With such a configuration, it is possible to provide a resin composition that can effectively suppress back exposure while achieving low dielectric properties. In particular, in this embodiment, it is preferable to use a resin composition containing an ultraviolet absorber and a nonmetallic organic dye. By using both an ultraviolet absorber and a nonmetallic organic dye, the light transmittance can be effectively lowered even if the total amount of both components used in the resin composition is relatively small. It becomes possible to provide a resin composition that can effectively suppress back exposure while achieving the desired characteristics. Furthermore, by precisely adjusting the content and blending ratio of ultraviolet absorbers and nonmetallic organic dyes, we have created a resin composition that has excellent heat resistance and can effectively suppress back exposure while maintaining low dielectric properties. It becomes possible to provide things.

<Thermosetting compound>
The resin composition of this embodiment contains a thermosetting compound. The thermosetting compound is usually a main component of the cured product of this embodiment.
The thermosetting compounds used in this embodiment include maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, compounds containing (meth)allyl groups, and polyphenylene ethers containing two or more carbon-carbon unsaturated double bonds. It is preferable to include one or more selected from the group consisting of a compound, a polymer having a structural unit represented by formula (V), and a cyanate ester compound, such as a maleimide compound, an epoxy compound, a phenol compound, and an oxetane resin. , a benzoxazine compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, a polymer having a structural unit represented by formula (V), and a cyanate ester compound. It is more preferable to contain at least one type selected from the group consisting of a maleimide compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and a cyanate ester compound. , a maleimide compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and a cyanate ester compound.
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

<<Maleimide compound>>
The resin composition of this embodiment may contain a maleimide compound. The resin composition of the present embodiment contains two or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) maleimides in one molecule. There are no particular limitations on the compound as long as it has a group, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
In this embodiment, the maleimide compound is preferably a compound represented by formulas (M0) to (M5), a maleimide compound (M6), or a compound represented by formula (M7), and a compound represented by formula (M0) is preferably used. More preferred are compounds such as
(In formula (M0), R ⁵¹ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵² each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer greater than or equal to 1.)
R ⁵¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, or a phenyl group; One of the methyl groups is more preferable, and a hydrogen atom is even more preferable.
R ⁵² is preferably a methyl group.
n ₁ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, even more preferably 1 or 2, and even more preferably 1.
The compound represented by formula (M0) may be one type or a mixture of two or more types. Examples of mixtures include mixtures of compounds in which _n1 is different, mixtures of compounds in which the types of substituents for ^R51 and/or ^R52 are different, and the bonding position of the maleimide group and the oxygen atom to the benzene ring (meta position, para position, Examples include mixtures of compounds having different positions (ortho positions), and mixtures of compounds having two or more of the above-mentioned different points combined. The same applies to the compounds represented by formulas (M1) to (M5), the maleimide compound (M6), and the compound represented by formula (M7) below.

(In formula (M1), R ^M1 , R ^M2 , R ^M3 , and R ^M4 each independently represent a hydrogen atom or an organic group. R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R ^M7 and R ^M8 are each independently an alkyl group. mx is 1 or 2 , and lx is 0 or 1. R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group. R ^M11 , R ^M12 , R ^M13 , and R ^M14 each independently represent a hydrogen atom or represents an organic group.R ^M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. , represents an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20. )

R ^M1 , R ^M2 , R ^M3 , and R ^M4 in the formula each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group, especially a methyl group. R ^M1 and R ^M3 are each independently preferably an alkyl group, and R ^M2 and R ^M4 are preferably a hydrogen atom.
R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
Ar ^M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, an anthracenediyl group, more preferably a phenylene group, still more preferably a m-phenylene group. Ar ^M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, Ethyl group, propyl group, and butyl group are more preferable, and methyl group is particularly preferable. However, it is preferable that Ar ^M is unsubstituted.
A is a 4- to 6-membered alicyclic group, and more preferably a 5-membered alicyclic group (preferably a group that forms an indane ring when combined with a benzene ring). R ^M7 and R ^M8 each independently represent an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
mx is 1 or 2, preferably 2.
lx is 0 or 1, preferably 1.
R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is more preferred. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
R ^M11 , R ^M12 , R ^M13 , and R ^M14 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group, especially a methyl group. R ^M12 and R ^M13 are each independently preferably an alkyl group, and R ^M11 and R ^M14 are preferably a hydrogen atom.
R ^M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. represents an aryloxy group, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 6 to 10 carbon atoms. is preferably an aryl group.
px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
nx represents an integer from 1 to 20. nx may be an integer of 10 or less.
The resin composition of the present embodiment may contain only one type of compound (M1) represented by formula (M1), or may contain two or more types of compounds having at least different values of nx. You can stay there. When two or more types are included, the average value of nx (average number of repeating units) n in the compound (M1) represented by formula (M1) in the resin composition has a low melting point (low softening point) and a melt viscosity. In order to have a low value and excellent handling properties, it is preferably 0.92 or more, more preferably 0.95 or more, even more preferably 1.0 or more, and 1.1 or more. It is more preferable that there be. Further, n is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, even more preferably 6.0 or less, and 5. It may be 0 or less. The same applies to equations (M1-2) and the like that will be described later.

The compound (M1) represented by formula (M1) is preferably a compound represented by formula (M1-1) below.
(In formula (M1-1), R ^M21 , R ^M22 , R ^M23 , and R ^M24 each independently represent a hydrogen atom or an organic group. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl R ^M27 , R ^M28 , R ^M29 , and R ^M30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. R ^M33 , R ^M34 , R ^M35 , and R ^M36 each independently represent a hydrogen atom or an organic group. R ^M37 , R ^M38 , and R ^M39 each independently represent a hydrogen atom or an alkyl group. nx is Represents an integer between 1 and 20.)

R ^M21 , R ^M22 , R ^M23 , and R ^M24 in the formula each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group. R ^M21 and R ^M23 are preferably alkyl groups, and R ^M22 and R ^M24 are preferably hydrogen atoms.
R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
R ^M27 , R ^M28 , R ^M29 , and R ^M30 each independently represent a hydrogen atom or an organic group, and preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group.
R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
R ^M33 , R ^M34 , R ^M35 , and R ^M36 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group.
R ^M33 and R ^M36 are preferably hydrogen atoms, and R ^M34 and R ^M35 are preferably alkyl groups.
R ^M37 , R ^M38 , and R ^M39 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferable. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
nx represents an integer from 1 to 20. nx may be an integer of 10 or less.

The compound represented by formula (M1-1) is preferably a compound represented by formula (M1-2) below.
(In formula (M1-2), R ^M21 , R ^M22 , R ^M23 , and R ^M24 each independently represent a hydrogen atom or an organic group. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl R ^M27 , R ^M28 , R ^M29 , and R ^M30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. R ^M33 , R ^M34 , R ^M35 , and R ^M36 each independently represent a hydrogen atom or an organic group. R ^M37 , R ^M38 , and R ^M39 each independently represent a hydrogen atom or an alkyl group. nx is Represents an integer between 1 and 20.)

In formula (M1-2), ^RM21 , ^RM22 , ^RM23 , ^RM24 , RM25, ^RM26 , ^RM27 , ^RM28 , ^RM29 , ^RM30 ^, ^RM31 , ^RM32 , ^RM33 , ^RM34 , R ^M35 , R ^M36 , R ^M37 , R ^M38 , R ^M39 , and nx are R ^M21 , R ^M22 , R ^M23 , R ^M24 , R ^M25 , R ^M26 , R ^M27 in formula (M1-1), respectively; It is synonymous with R ^M28 , R ^M29 , R ^M30 , R ^M31 , R ^M32 , R ^M33 , R ^M34 , R ^M35 , R ^M36 , R ^M37 , R ^M38 , R ^M39 , and nx, and the preferred ranges are also the same. .

The compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-3), and more preferably a compound represented by the following formula (M1-4).
(In formula (M1-3), nx represents an integer from 1 to 20.)
nx may be an integer of 10 or less.
(In formula (M1-4), nx represents an integer from 1 to 20.)
nx may be an integer of 10 or less.

The molecular weight of the compound (M1) represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low dielectric properties and low water absorption. Further, the molecular weight of the compound (M1) represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, and preferably 5,000 or less. More preferably, it is 4000 or less. By setting it below the above-mentioned upper limit, the heat resistance and handleability of the obtained cured product tend to be further improved.

(In formula (M2), R ⁵⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)
n ₄ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, even more preferably 1 or 2, and may be 1.
The compound represented by formula (M2) may be a mixture of compounds in which n ₄ is different, and is preferably a mixture. Further, as described in the section of the compound represented by formula (M0), it may be a mixture of compounds having different parts.
(In formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer of 1 to 10.)
R ⁵⁵ is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, or phenyl group; One of the methyl groups is more preferable, and a hydrogen atom is even more preferable.
n ₅ is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
The compound represented by formula (M3) may be a mixture of compounds having different n ₅ values, and is preferably a mixture. Further, as described in the section of the compound represented by formula (M0), it may be a mixture of compounds having different parts.
(In formula (M4), R ⁵⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group.)

(In formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ represents an integer greater than or equal to 1.)
R ⁵⁸ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, or a phenyl group; One of the methyl groups is more preferable, and a hydrogen atom is even more preferable.
R ⁵⁹ is preferably a methyl group.
n ₆ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, even more preferably 1 or 2, and may be 1.
The compound represented by formula (M5) may be a mixture of compounds having different n ₆ values, and is preferably a mixture. Further, as described in the section of the compound represented by formula (M0), it may be a mixture of compounds having different parts.

The maleimide compound (M6) is a compound having a structural unit represented by formula (M6) and maleimide groups at both ends of the molecular chain.
(In formula (M6), R ⁶¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ⁶² is R ⁶³ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. Represents a chain or branched alkyl group, or a straight or branched alkenyl group having 2 to 16 carbon atoms. Each n independently represents an integer of 0 to 10.)
For details of the maleimide compound (M6) and its manufacturing method, the description in paragraphs 0061 to 0066 of International Publication No. 2020/262577 can be referred to, the contents of which are incorporated herein.

As described for the compound represented by formula (M0), the maleimide compound (M6) may be a mixture of compounds different in other parts.

(In the above formula (M7), R ¹ each independently represents the alkyl group, R ² each independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; represents an aryl group, aryloxy group or arylthio group; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and R ⁵ and R ⁶ are One is a hydrogen atom, the other is a methyl group,
X ¹ is the following formula (x):
(In formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ is each independently an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or It represents a mercapto group, and t represents an integer from 0 to 4.)
represents a substituent represented by, r is the average value of the number of substitutions of X ¹ per benzene ring to which X ¹ is bonded, and represents a number from 0 to 4, p is an integer from 1 to 3 , q represents an integer from 0 to 4, and k represents an integer from 1 to 100. )
Further, in the above formula (1), when p is an integer of 2 or more, a plurality of R ^1s may be the same or different. When q is an integer of 2 or more, a plurality of R ² 's may be the same or different. When t is an integer of 2 or more, a plurality of R ^9s may be the same or different.
The compound represented by formula (M7) may be a mixture of compounds with different k, and is preferably a mixture. Further, as described in the section of the compound represented by formula (M0), it may be a mixture of compounds having different parts.
For details of the compound represented by formula (M7), the description in Japanese Patent No. 7160151 can be referred to, the contents of which are incorporated herein.

The maleimide compound may be produced by a known method, or a commercially available product may be used. Commercially available products include, for example, "BMI-80" manufactured by K.I. Kasei Co., Ltd. as a compound represented by formula (M0), and "NE-X-9470S" manufactured by DIC Corporation as a compound represented by formula (M1). ", the compound represented by formula (M2) is "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the compound represented by formula (M3) is "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., formula (M4) The compound represented by formula (M5) is "BMI-70" manufactured by K-I Kasei Co., Ltd., the compound represented by formula (M5) is "MIR-5000" manufactured by Nippon Kayaku Co., Ltd., and the maleimide compound (M6) is manufactured by Nippon Kayaku Co., Ltd. Examples of the compound represented by formula (M7) include "NE-X-9500" manufactured by DIC Corporation.

Examples of maleimide compounds other than those mentioned above include compounds having two or more maleimide groups, specifically m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl) ) Propane, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bis Examples include maleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers thereof, and prepolymers of these maleimides and amines.

When the resin composition of the present embodiment contains a maleimide compound, the lower limit of its content is preferably 1 part by mass or more, and 5 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more. More preferably, the amount is 30 parts by mass or more, particularly preferably 30 parts by mass or more. When the content of the maleimide compound is 1 part by mass or more, the flame resistance of the obtained cured product tends to improve. Further, the upper limit of the content of the maleimide compound is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and 60 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably at most 50 parts by mass, even more preferably at most 40 parts by mass. When the content of the maleimide compound is 90 parts by mass or less, the metal foil peel strength and low water absorption tend to improve.
The resin composition in this embodiment may contain only one type of maleimide compound, or may contain two or more types of maleimide compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

<<Epoxy compound>>
The resin composition of this embodiment may contain an epoxy compound.
An epoxy compound is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) epoxy groups in one molecule. Alternatively, there is no particular limitation as long as it is a resin, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of epoxy compounds include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, and aralkyl epoxy resin. Novolac type epoxy resin, biphenylaralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol Aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, butadiene, etc. Examples include compounds in which bonds are epoxidized, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. By using these, the moldability and adhesion of the resin composition are improved. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenylaralkyl epoxy resins, naphthylene ether epoxy resins, polyfunctional phenol epoxy resins, and naphthalene epoxy resins are preferred; More preferably, it is a type epoxy resin.

The resin composition of the present embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an epoxy compound, the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is at least 2 parts by mass, and even more preferably 2 parts by mass or more. When the content of the epoxy compound is 0.1 part by mass or more, the peel strength and toughness of the metal foil tend to improve. When the resin composition of this embodiment contains an epoxy compound, the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less, and 30 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. The amount is more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, and may be at most 8 parts by mass, and may be at most 5 parts by mass. When the content of the epoxy compound is 50 parts by mass or less, the electrical properties of the obtained cured product tend to improve.
The resin composition in this embodiment may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also have a structure that does not substantially contain an epoxy compound. "Substantially free" means that the content of the epoxy compound is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, based on 100 parts by mass of resin solids in the resin composition. , and even less than 0.001 part by mass.

<<Phenol compounds>>
The resin composition of this embodiment may contain a phenol compound.
The phenol compound has one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) phenolic hydroxyl groups in one molecule. The phenol compound is not particularly limited, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of the phenol compound include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac phenol. Resin, biphenylaralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenolic resin, Examples include naphthol aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, alicyclic phenolic resins, polyol-type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins. Among these, from the viewpoint of further improving the flame resistance of the obtained cured product, at least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin. Preferably it is a seed.

The resin composition of the present embodiment preferably contains a phenol compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a phenol compound, the content thereof is preferably 0.1 part by mass or more, and 1 part by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is at least 2 parts by mass, and even more preferably 2 parts by mass or more. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass or less. There may be.
The resin composition in this embodiment may contain only one type of phenol compound, or may contain two or more types of phenol compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also have a structure that does not substantially contain a phenol compound. "Substantially free" means that the content of the phenol compound is less than 0.1 parts by mass based on 100 parts by mass of resin solids in the resin composition.

<<Oxetane resin>>
The resin composition of this embodiment may contain oxetane resin.
The oxetane resin is particularly a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2). There are no limitations, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of the oxetane resin include oxetane, alkyloxetane (for example, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), OXT-121 (manufactured by Toagosei Co., Ltd.) ), etc.

The resin composition of this embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an oxetane resin, the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more based on 100 parts by mass of resin solids in the resin composition. More preferably, the amount is 2 parts by mass or more. When the content of the oxetane resin is 0.1 part by mass or more, the metal foil peel strength and toughness tend to improve. When the resin composition of this embodiment contains an oxetane resin, the upper limit of the content of oxetane resin is preferably 50 parts by mass or less, and 30 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition. It is more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, and may be at most 5 parts by mass. When the content of the oxetane resin is 50 parts by mass or less, the electrical properties of the resulting cured product tend to improve.
The resin composition in this embodiment may contain only one type of oxetane resin, or may contain two or more types of oxetane resin. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain oxetane resin. "Substantially free" means that the content of oxetane resin is less than 0.1 parts by mass based on 100 parts by mass of resin solid content in the resin composition.

<<Benzoxazine compound>>
The resin composition of this embodiment may contain a benzoxazine compound.
The benzoxazine compound includes 2 or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) dihydrobenzoxazines in one molecule. Any compound having a ring is not particularly limited, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of benzoxazine compounds include bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.). ), etc.

The resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a benzoxazine compound, the content thereof is preferably 0.1 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of resin solids in the resin composition. It is preferable that
The resin composition in this embodiment may contain only one type of benzoxazine compound, or may contain two or more types of benzoxazine compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain a benzoxazine compound. "Substantially free" means that the content of the benzoxazine compound is less than 0.1 parts by mass based on 100 parts by mass of resin solid content in the resin composition.

<<Compound containing (meth)allyl group>>
The resin composition of this embodiment preferably contains a compound containing a (meth)allyl group, and more preferably contains a compound containing an allyl group.
Further, the compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups.
The compound containing a (meth)allyl group preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, an allyl compound having a glycoluril structure, and diallyl phthalate, It is more preferable to contain at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, and an allyl compound having a glycoluril structure, and more preferably an allyl group-substituted nadimide compound, and an alkenyl More preferred are nadimide compounds.

When the resin composition of the present embodiment contains a compound containing a (meth)allyl group, its molecular weight is preferably 195 or more, more preferably 300 or more, and even more preferably 400 or more. , more preferably 500 or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low dielectric properties and heat resistance. The molecular weight of the compound containing a (meth)allyl group is also preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less, and even more preferably 800 or less. By setting it below the above-mentioned upper limit, the low thermal expansion property of the obtained cured product tends to be further improved.

When the resin composition of the present embodiment contains a compound containing a (meth)allyl group, the content thereof is preferably 1 part by mass or more, and 3 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferably at least 5 parts by mass, even more preferably at least 5 parts by mass, and may be at least 10 parts by mass. By setting the content of the compound containing a (meth)allyl group to the above lower limit or more, the moldability of the resin composition tends to be excellent, and the heat resistance of the resulting cured product tends to be further improved. Further, the upper limit of the content of the compound containing a (meth)allyl group is preferably 40 parts by mass or less, and preferably 30 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. More preferably, the amount is 20 parts by mass or less. By controlling the content of the compound containing a (meth)allyl group to the above-mentioned upper limit or less, the low thermal expansion properties of the resulting cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of compound containing a (meth)allyl group, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain a compound containing a (meth)allyl group. "Substantially free" means that the content of the compound containing a (meth)allyl group is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition.

<<<Allyl isocyanurate compound>>>
The allyl isocyanurate compound is not particularly defined as long as it has two or more allyl groups and an isocyanurate ring (nurate skeleton), but a compound represented by formula (TA) is preferable. .
Formula (TA)
(In formula (TA), ^RA represents a substituent).

In formula (TA), R ^A represents a substituent, and is preferably a substituent having a formula weight of 15 to 500.

A first example of R ^A is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. A resin composition capable of obtaining a cured product having excellent crosslinkability and high toughness by using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. can be provided. Thereby, even if the resin composition does not include a base material such as glass cloth, it is possible to suppress cracking during etching treatment or the like.
From the viewpoint of improving handling properties, the number of carbon atoms in the alkyl group and/or alkenyl group is preferably 3 or more, more preferably 8 or more, may be 12 or more, and is preferably 18 or less. It is thought that this improves the resin flowability of the resin composition, resulting in better circuit filling properties when creating a multilayer circuit board or the like using the resin composition of this embodiment.

A second example of R ^A is a group containing an allyl isocyanurate group. When R ^A contains an allyl isocyanurate group, the compound represented by formula (TA) is preferably a compound represented by formula (TA-1).
Formula (TA-1)
(In formula (TA-1), R ^A2 is a divalent linking group.)

In formula (TA-1), R ^A2 is preferably a divalent linking group having a formula weight of 54 to 250, and a divalent linking group having a formula weight of 54 to 250 and having carbon atoms at both ends. is more preferable, and an aliphatic hydrocarbon group having 2 to 20 carbon atoms is even more preferable (however, the aliphatic hydrocarbon group may contain an ether group, and may have a hydroxyl group). ). More specifically, R ^A2 is preferably a group represented by any of the following formulas (i) to (iii).
(In the formulas (i) to (iii), p ^c1 represents the number of repeating units of the methylene group and is an integer from 2 to 18. ^{p c2} represents the number of repeating units of the oxyethylene group and is 0 or 1. .* is the binding site.)
The p ^c1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 5.
The p ^c2 may be 0 or 1, but is preferably 1.

Preferably, R ^A2 is the first example.

In this embodiment, it is desirable that the reactive group (allyl group) equivalent of the compound represented by formula (TA) is 1000 or less. It is considered that if the equivalent is 1000 or less, a high Tg can be obtained more reliably.
Examples of the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, and the like. Further, examples of the alkenyl group having 2 to 22 carbon atoms include an allyl group and a decenyl group.

Specific examples of the compound represented by formula (TA) include triallylisocyanurate, 5-octyl-1,3-diallylisocyanurate, 5-dodecyl-1,3-diallylisocyanurate, 5-tetradecyl- 1,3-diallylisocyanurate, 5-hexadecyl-1,3-diallylisocyanurate, 5-octadecyl-1,3-diallylisocyanurate, 5-eicosyl-1,3-diallylisocyanurate, 5-docosyl-1, Examples include 3-diallylisocyanurate and 5-decenyl-1,3-diallylisocyanurate. These may be used alone or in combination of two or more, or may be used as a prepolymer.

The method for producing the compound represented by formula (TA) is not particularly limited, but for example, diallylisocyanurate and alkyl halide are mixed in an aprotic polar solvent such as N,N'-dimethylformamide, and sodium hydroxide is added. It can be obtained by reacting at a temperature of about 60°C to 150°C in the presence of a basic substance such as , potassium carbonate, or triethylamine.

Furthermore, commercially available compounds can also be used as the compound represented by formula (TA). Commercially available products include, but are not particularly limited to, L-DAIC manufactured by Shikoku Kasei Kogyo Co., Ltd., for example. Examples of triallyl isocyanurate include TAIC manufactured by Mitsubishi Chemical Corporation. Examples of the compound represented by formula (TA-1) include DD-1 manufactured by Shikoku Kasei Kogyo Co., Ltd.

The molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more. It is more preferable that By setting the molecular weight to the lower limit value or more, the resulting cured product tends to have improved low dielectric properties and heat resistance. Further, the molecular weight of the allyl isocyanurate compound (preferably a compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, More preferably, it is 800 or less. By controlling the molecular weight to be less than or equal to the upper limit value, the resulting cured product tends to have improved low thermal expansion properties.

When the resin composition of the present embodiment contains an allyl isocyanurate compound, the content thereof is preferably 1 part by mass or more, and 3 parts by mass or more based on 100 parts by mass of resin solids in the resin composition. The amount is more preferably 5 parts by mass or more, and may be 10 parts by mass or more. By setting the content of the allyl isocyanurate compound to the above lower limit or more, the moldability of the resin composition tends to be excellent, and the heat resistance of the resulting cured product tends to be further improved. Further, the upper limit of the content of the allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably less than parts by mass. By controlling the content of the allyl isocyanurate compound to be less than or equal to the above upper limit, the low thermal expansion properties of the resulting cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of allyl isocyanurate, or may contain two or more types of allyl isocyanurate. When two or more types are included, it is preferable that the total amount falls within the above range.

<<<Allyl group-substituted nadimide compound>>>
Examples of allyl-substituted nadimide compounds include compounds having one or more allyl-substituted nadimide groups in the molecule (preferably compounds having one or more alkenyl-substituted nadimide groups in the molecule (alkenylnadimide compounds)) ), it is not particularly limited. A specific example thereof is a compound represented by the following formula (AN).
Formula (AN)
(In formula (AN), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₂ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, Represents a naphthylene group or a group represented by formula (AN-2) or (AN-3).
Formula (AN-2)
(In formula (AN-2), R ₃ is represented by a methylene group, an isopropylidene group, -C(=O)-, -O-, -S-, or -S(=O) ₂ - (Represents a group.)
Formula (AN-3)
(In formula (AN-3), R ₄ each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

Moreover, a commercially available compound can also be used as the compound represented by formula (AN). Commercially available compounds include, but are not particularly limited to, compounds represented by the formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)), compounds represented by the formula (AN-5), Examples include compounds such as BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.). These may be used alone or in combination of two or more.
Formula (AN-4)
Formula (AN-5)

The molecular weight of the allyl group-substituted nadimide compound (preferably the compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may be 550 or more. By setting the molecular weight of the allyl group-substituted nadimide compound to the above lower limit or more, the resulting cured product tends to have improved low dielectric properties, low thermal expansion properties, and heat resistance. The molecular weight of the allyl group-substituted nadimide compound (preferably a compound represented by formula (AN)) is also preferably 1,500 or less, more preferably 1,000 or less, even more preferably 800 or less, It may be 700 or less, or 600 or less. By controlling the molecular weight of the allyl group-substituted nadimide compound to be less than or equal to the above upper limit, the moldability of the resin composition and the peel strength of the obtained cured product tend to be further improved.

When the resin composition of the present embodiment contains an allyl-substituted nadimide compound (preferably a compound represented by formula (AN)), the content thereof is 0 parts by mass based on 100 parts by mass of resin solid content in the resin composition. .1 part by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass or less. There may be. By controlling the content of the allyl group-substituted nadimide compound to be less than or equal to the above upper limit, the moldability of the resin composition and the peel strength of the obtained cured product tend to be further improved.
The resin composition of the present embodiment may contain only one kind of allyl group-substituted nadimide compound, or may contain two or more kinds of allyl group-substituted nadimide compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain the allyl group-substituted nadimide compound. "Substantially free" means that the content of the allyl group-substituted nadimide compound is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition.

<<<Allyl compound having glycoluril structure>>>
The allyl compound having a glycoluril structure is not particularly limited as long as it contains a glycoluril structure and two or more allyl groups, and a compound represented by formula (GU) is preferred.
Formula (GU)
(In formula (GU), each R is independently a hydrogen atom or a substituent, and at least two of R are groups containing an allyl group.)
In formula (GU), each R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. Preferably, it is an allyl group.
In formula (GU), R is preferably a group containing three or four allyl groups, and more preferably a group containing four allyl groups.

A specific example of the compound represented by formula (GU) is 1,3,4,6-tetraallylglycoluril (a compound in which all R's are allyl groups in formula (GU)).

Further, as the compound represented by formula (GU), a commercially available one can also be used. Commercially available products include, but are not particularly limited to, TA-G manufactured by Shikoku Kasei Kogyo Co., Ltd., for example.

The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, even more preferably 250 or more, It may be 300 or more, or 400 or more. By setting the molecular weight of the allyl compound having a glycoluril structure to the above lower limit or more, the low dielectric properties and heat resistance of the resulting cured product tend to be further improved. The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is also preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less. It is preferably 700 or less, or may be 600 or less. By controlling the molecular weight of the allyl compound having a glycoluril structure to be less than or equal to the above upper limit, the resulting cured product tends to have better low thermal expansion properties.

When the resin composition of the present embodiment contains an allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)), the content thereof is based on 100 parts by mass of resin solid content in the resin composition. , is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more. By setting the content of the allyl compound having a glycoluril structure to the above lower limit or more, the low dielectric properties and heat resistance of the resulting cured product tend to be further improved. Further, the upper limit of the content of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is 40 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. The amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and may be 20 parts by mass or less. By controlling the content of the allyl compound having a glycoluril structure to the above upper limit value or less, the low thermal expansion property of the obtained cured product tends to be further improved.
The resin composition of this embodiment may contain only one type of allyl compound having a glycoluril structure, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<<Polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds>>
The resin composition of this embodiment may contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at the terminal, and a (meth)acrylic group at the terminal, More preferably, it is a polyphenylene ether compound having two or more groups selected from the group consisting of a maleimide group, a (meth)allyl group, and a vinylbenzyl group; More preferably, it is a polyphenylene ether compound having two or more selected groups. By using these polyphenylene ether compounds, it tends to be possible to more effectively improve the low dielectric properties (low dielectric constant and/or low dielectric loss tangent), low water absorption, etc. of printed wiring boards and the like.
These details will be explained below.

The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is exemplified by a compound having a phenylene ether skeleton represented by the following formula (X1).

(In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom. )

The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds has the formula (X2):
(In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different and represent an alkyl group or a phenyl group having 6 or less carbon atoms. R ³¹ , R ³² , and R ³³ may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
A repeating unit represented by and/or formula (X3):
(In formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ may be the same or different, hydrogen atom, alkyl having 6 or less carbon atoms) or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

A polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a modified polyphenylene ether compound (hereinafter referred to as a "modified polyphenylene ether compound (g )” is preferable, and the modified polyphenylene ether has two or more groups selected from the group consisting of (meth)acrylic group, maleimide group, (meth)allyl group, and vinylbenzyl group at the terminal. It is more preferably a compound, and more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of a (meth)acrylic group, a maleimide group, and a vinylbenzyl group at its terminal. By employing such a modified polyphenylene ether compound (g), it becomes possible to further reduce the dielectric loss tangent (Df) of the cured product of the resin composition, and to increase low water absorption and metal foil peel strength. . These may be used alone or in combination of two or more.

Examples of the modified polyphenylene ether compound (g) include polyphenylene ether compounds represented by formula (OP).
(In formula (OP), X represents an aromatic group, -(Y-O) _n1 - represents a polyphenylene ether structure, n1 represents an integer of 1 to 100, and n2 represents an integer of 1 to 4. Rx is a group represented by formula (Rx-1) or formula (Rx-2).)
(In formula (Rx-1) and formula (Rx-2), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. *: It is a bonding site with an oxygen atom. Mc each independently represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6.)

When n ₁ and/or n ₂ are integers of 2 or more, the n ₁ structural units (YO) and/or the n ₂ structural units may be the same or different. n ₂ is preferably 2 or more, more preferably 2.

In formulas (Rx-1) and (Rx-2), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.
R ¹ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
The number of carbon atoms in each of the alkyl group, alkenyl group, or alkynyl group as R ¹ , R ² , and R ³ is preferably 5 or less, more preferably 3 or less.

In formula (Rx-1), r represents an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and preferably an integer of 1 to 3. More preferably, it is 1 or 2, even more preferably 1.

In formula (Rx-1), Mc each independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, and a linear chain having 1 to 10 carbon atoms. or a branched alkyl group, more preferably a methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, octyl group, or nonyl group, and a methyl group, an ethyl group , isopropyl group, isobutyl group, or t-butyl group are more preferable.
In formula (Rx-1), z represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and most preferably 0.

A specific example of the group represented by formula (Rx-1) is a vinylbenzyl group, and a specific example of the group represented by formula (Rx-2) is a (meth)acryloyl group.

As the modified polyphenylene ether compound (g), a compound represented by formula (OP-1) is preferred.
(In formula (OP-1), X represents an aromatic group, -(Y-O)n ₂ - represents a polyphenylene ether structure, and R ¹ , R ² and R ³ are each independently, It represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 1 to 4.)
When n ₂ and/or n ₃ are integers of 2 or more, the n ₂ structural units (YO) and/or the n ₃ structural units may be the same or different. n ₃ is preferably 2 or more, more preferably 2.

The modified polyphenylene ether compound (g) in this embodiment is preferably a compound represented by formula (OP-2).
Here, -(O-X-O)- is the formula (OP-3):
(In formula (OP-3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ⁷ , R ⁸ and R ⁹ may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
and/or formula (OP-4):
(In formula (OP-4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and each has a hydrogen atom and a carbon number of 6 or less. is an alkyl group or phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Moreover, -(YO)- is the formula (OP-5):
(In formula (OP-5), R ²⁰ and R ²¹ may be the same or different and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ²² and R ²³ may be the same or different, It is preferably represented by a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. In particular, by setting R ²⁰ and R ²¹ each independently to a group having one or more methyl group and/or cyclohexyl group, the resulting resin molecule will have high rigidity, and molecules with high rigidity will have high rigidity. It is preferable because it has a lower mobility than a low-temperature molecule, so the relaxation time during dielectric relaxation is longer, and the low dielectric properties (Dk and/or Df) are improved.
An example of formula (OP-5) is the following structure.
Regarding the polyphenylene compound having the above structure, the description in JP-A-2019-194312 can be referred to, and the contents thereof are incorporated herein.

In formula (OP-2), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100. a and b are each independently preferably an integer of 0 to 50, more preferably an integer of 1 to 30, and preferably an integer of 1 to 10. When a and/or b is an integer of 2 or more, 2 or more -(YO)- may each independently be an array of one type of structure, or two or more types of structures may be a block or They may be arranged randomly.
Furthermore, when multiple types of compounds represented by formula (OP-2) are included, the average value of a is preferably 1<a<10, and the average value of b is preferably 1<b<10. .

-A- in formula (OP-4) is, for example, a methylene group, ethylidene group, 1-methylethylidene group, 1,1-propylidene group, 1,4-phenylenebis(1-methylethylidene) group, 1, Examples include, but are not limited to, divalent organic groups such as 3-phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthylmethylene group, and 1-phenylethylidene group. .

In the compound represented by the above formula (OP-2), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ and R ²¹ are alkyl groups having 3 or less carbon atoms, and R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² and R ²³ are hydrogen atoms or alkyl groups having 3 or less carbon atoms A polyphenylene ether compound is preferable, and in particular, -(O-X-O)- represented by formula (OP-3) or formula (OP-4) is represented by formula (OP-9) or formula (OP-10). , and/or formula (OP-11), and -(YO)- represented by formula (OP-5) is preferably formula (OP-12) or formula (OP-13) . When a and/or b are integers of 2 or more, -(Y-O)- of 2 or more each independently represents a structure in which two or more of formula (OP-12) and/or formula (OP-13) are arranged. Alternatively, it may have a structure in which formula (OP-12) and formula (OP-13) are arranged in blocks or randomly.

(In formula (OP-10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different and are a hydrogen atom or a methyl group. -B- is a straight line having 20 or less carbon atoms. It is a chain, branched, or cyclic divalent hydrocarbon group.)
Specific examples of -B- include the same examples as -A- in formula (OP-4).
(In formula (OP-11), -B- is a straight chain, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)
Specific examples of -B- include the same examples as -A- in formula (OP-4).

The polyphenylene ether compound used in this embodiment is more preferably a compound represented by formula (OP-14) and/or a compound represented by formula (OP-15). It is more preferable that the compound is
(In formula (OP-14), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)
a and b in formula (OP-14) each independently have the same meaning as a and b in formula (OP-2), and the preferred ranges are also the same.
(In formula (OP-15), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)
a and b in formula (OP-15) each independently have the same meaning as a and b in formula (OP-2), and the preferred ranges are also the same.

The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds may be produced by a known method, or a commercially available product may be used. As a commercially available product, for example, "SA9000" manufactured by SABIC Innovative Plastics is a modified polyphenylene ether compound having a methacrylic group at the terminal end. Examples of modified polyphenylene ether compounds having a vinylbenzyl group at the end include "OPE-2St1200" and "OPE-2st2200" manufactured by Mitsubishi Gas Chemical. In addition, as a modified polyphenylene ether compound having a vinylbenzyl group at the end, a polyphenylene ether compound having a hydroxyl group at the end, such as "SA90" manufactured by SABIC Innovative Plastics, was modified to a vinylbenzyl group using vinylbenzyl chloride or the like. You can also use something.

In addition, details of polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds can be found in JP-A No. 2006-028111, JP-A No. 2018-131519, WO2019-138992, and WO2022-054303. The contents of these documents are incorporated into the present specification.

The number average molecular weight of a polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds in terms of polystyrene by GPC (gel permeation chromatography) method (details will be described later) (according to the method described in Examples) is preferably 500 or more and 3,000 or less. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of this embodiment is formed into a coating film. When the number average molecular weight is 3,000 or less, the solubility in a solvent tends to be further improved.
In addition, the weight average molecular weight of a polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) in terms of polystyrene by GPC (for details, follow the method described in the Examples below) ) is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By setting the above lower limit or more, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting the above upper limit or less, the varnish etc. described below The solubility, low viscosity, and moldability of the resin composition in the solvent during production tend to be further improved.
Further, in the case of the modified polyphenylene ether compound (g), the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and 400 to 2500 g. It is more preferable that By setting it above the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above upper limit, the solubility, low viscosity, and moldability of the resin composition in a solvent tend to be further improved.

When the resin composition of the present embodiment contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is , preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and 15 parts by mass, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is above, and even more preferable that it is 20 parts by mass or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low water absorption and low dielectric properties (Dk and/or Df). Further, the upper limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 70 parts by mass or less, and 60 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably at most 50 parts by mass, even more preferably at most 40 parts by mass, even more preferably at most 35 parts by mass, and even more preferably at most 30 parts by mass. It is even more preferable. When the amount is below the upper limit, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.
The resin composition in this embodiment may contain only one type of polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<<Polymer (V) having a structural unit represented by formula (V)>>
The resin composition of the present embodiment may include a polymer (V) having a structural unit represented by formula (V). By including the polymer (V) having the structural unit represented by formula (V), a resin composition having excellent low dielectric properties (low dielectric constant and/or low dielectric loss tangent) can be obtained.
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
The aromatic hydrocarbon linking group may be a group consisting only of an aromatic hydrocarbon that may have a substituent, or a group consisting of an aromatic hydrocarbon that may have a substituent and another linking group. It may be a group consisting of a combination of. The aromatic hydrocarbon linking group is preferably a group consisting only of aromatic hydrocarbons that may have substituents. The substituent that the aromatic hydrocarbon may have is a substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, hydroxy groups, amino groups, carboxy groups, halogen atoms, etc.). Further, it is preferable that the aromatic hydrocarbon has no substituent.
The aromatic hydrocarbon linking group is usually a divalent linking group.

Specific examples of the aromatic hydrocarbon linking group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent, Among these, a phenylene group which may have a substituent is preferred. The above-mentioned substituent Z is exemplified as the substituent, but it is preferable that groups such as the above-mentioned phenylene group have no substituent.

The structural unit represented by formula (V) is the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). More preferably, at least one is included. Note that * in the following formula represents the bonding position. Further, hereinafter, the constituent units represented by formulas (V1) to (V3) may be collectively referred to as "constituent unit (a)."

In formulas (V1) to (V3), L ¹ is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms). Specifically, examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent. A phenylene group is preferred. The above-mentioned substituent Z is exemplified as the substituent, but it is preferable that groups such as the above-mentioned phenylene group have no substituent.
The compound forming the structural unit (a) is preferably a divinyl aromatic compound, such as divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. It will be done. Among them, divinylbenzene is particularly preferred. One type of these divinyl aromatic compounds may be used, or two or more types may be used as necessary.

As mentioned above, the polymer (V) having a structural unit represented by formula (V) may be a homopolymer of the structural unit (a), but it may also be a copolymer with a structural unit derived from another monomer. It may be a combination.
When the polymer (V) having the structural unit represented by formula (V) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 3 mol % or more, and 5 mol % or more. % or more, more preferably 10 mol% or more, and may be 15 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, and 60 mol% or less. % or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, and furthermore, It may be 25 mol% or less, or 20 mol% or less.

As the structural unit derived from other monomers, the structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound) is exemplified.

The structural unit (b) derived from the monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).

In formula (V4), L ² is an aromatic hydrocarbon linking group, and a preferred example is the above-mentioned example of L ¹ .
R ^V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). When R ^V1 is a hydrocarbon group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. R ^V1 and L ² may have the above-mentioned substituent Z.

When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include styrene, Vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl; o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinyl Examples include nuclear alkyl-substituted vinyl aromatic compounds such as benzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compound exemplified here may have the above-mentioned substituent Z as appropriate. Further, these monovinyl aromatic compounds may be used alone or in combination of two or more.

When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) shall be 10 mol% or more. is preferable, more preferably 15 mol% or more, furthermore 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 75 mol%. It may be more than that. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.

The polymer (V) having the structural unit represented by formula (V) may have other structural units other than the structural unit (a) and the structural unit (b). Examples of other structural units include a structural unit (c) derived from a cycloolefin compound. Examples of the cycloolefin compound include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds condensed with aromatic rings such as indene and acenaphthylene. etc. can be mentioned. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of JP-A-2018-039995, the contents of which are incorporated herein. In addition, the cycloolefin compound illustrated here may further have the above-mentioned substituent Z.

When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) shall be 10 mol% or more. is preferable, more preferably 20 mol% or more, and even more preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, may be 50 mol% or less, and may be 30 mol% or less. It may be the following.

Even if the polymer (V) having the structural unit represented by formula (V) further incorporates a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compound). good. Examples of other polymerizable compounds (monomers) include compounds containing three vinyl groups. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, ethylene glycol diacrylate, butadiene, etc. may be mentioned. The copolymerization ratio (d) of the structural unit (d) derived from another polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less. is even more preferable.

As one embodiment of the polymer (V) having a structural unit represented by formula (V), a polymer containing the structural unit (a) as essential and at least one of the structural units (b) to (d) is Illustrated. Furthermore, an embodiment in which the total of structural units (a) to (d) accounts for 95 mol% or more, and further 98 mol% or more of the total structural units is exemplified.
Another embodiment of the polymer (V) having a structural unit represented by formula (V) is a structural unit in which the structural unit (a) is essential, and among all the structural units excluding the terminal, the structural unit contains an aromatic ring. is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.
In addition, when calculating the mol% per total structural unit, one structural unit refers to the monomer used to produce the polymer (V) having the structural unit represented by formula (V) (for example, divinyl Aromatic compounds, monovinyl aromatic compounds, etc.) shall originate from one molecule.

The method for producing the polymer (V) having the structural unit represented by the formula (V) is not particularly limited and may be any conventional method. For example, a raw material containing a divinyl aromatic compound (if necessary, a monovinyl aromatic compound compound, cycloolefin compound, etc.) and polymerization in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, a metal fluoride such as boron trifluoride or a complex thereof can be used.

The structure of the chain terminal of the polymer (V) having the structural unit represented by the formula (V) is not particularly limited, but when it comes to the group derived from the above divinyl aromatic compound, the structure of the following formula (E1) is One example is taking. Note that L ¹ in formula (E1) is the same as defined in formula (V1) above. * represents the bonding position.
*-CH=CH-L ¹ -CH=CH ₂ (E1)

When a group derived from a monovinyl aromatic compound becomes a chain terminal, a structure of the following formula (E2) may be adopted. L ² and R ^V1 in the formula each have the same meaning as defined in the above formula (V4). * represents the bonding position.
*-CH=CH-L ² -R ^V1 (E2)

The molecular weight of the polymer (V) having a structural unit represented by formula (V) is preferably a number average molecular weight Mn of 300 or more, more preferably 500 or more, and 1,000 or more. More preferably, it is 1,500 or more. The upper limit is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, and even more preferably 100,000 or less.
The molecular weight of the polymer (V) having a structural unit represented by formula (V) is preferably 3,000 or more, more preferably 5,000 or more, in weight average molecular weight Mw, 10, More preferably, it is 000 or more. By setting the above lower limit value or more, the excellent low dielectric properties of the polymer (V) having the structural unit represented by the formula (V), especially the Df and the low dielectric properties after moisture absorption, can be improved by curing the resin composition. You can make things work effectively. The upper limit is preferably 130,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 50,000 or less. By setting it below the above-mentioned upper limit, when a prepreg or a resin sheet is laminated on a circuit forming board, embedding failure tends to occur less easily.
The monodispersity (Mw/Mn) expressed by the ratio of weight average molecular weight Mw to number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less. . The lower limit is practically 1.1 or more, preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more.
The above Mw and Mn are measured in accordance with the description in the examples below.
When the resin composition of the present embodiment contains two or more kinds of polymers (V) having structural units represented by formula (V), it is preferable that Mw, Mn, and Mw/Mn of the mixture satisfy the above ranges.

The equivalent weight of vinyl groups in the polymer (V) having the structural unit represented by formula (V) is 200 g/eq. or more, preferably 230g/eq. More preferably, it is 250 g/eq. It is more preferable that it is above. Further, the equivalent weight of the vinyl group is 1200 g/eq. It is preferably less than 1000g/eq. It is more preferable that it is less than 800g/eq. Below, 600g/eq. Below, 400g/eq. Below, 300g/eq. It may be the following. By setting it to the above lower limit or more, the storage stability of the resin composition tends to improve, and the fluidity of the resin composition tends to improve. Therefore, moldability is improved, voids are less likely to occur during the formation of prepregs, etc., and a more reliable printed wiring board tends to be obtained. On the other hand, by setting it below the above upper limit, the heat resistance of the obtained cured product tends to improve.

In this specification, regarding the polymer (V) having a structural unit represented by formula (V), the compounds described in paragraphs 0029 to 0058 of International Publication No. 2017/115813 and their synthesis reaction conditions, etc. Compounds described in paragraphs 0013 to 0058 of JP-A-039995 and their synthesis reaction conditions, etc., compounds described in paragraphs 0008 to 0043 of JP-A-2018-168347 and their synthesis reaction conditions, etc., JP-A-2006-070136 Compounds described in paragraphs 0014 to 0042 of JP-A-2006-089683 and their synthesis reaction conditions, etc., compounds described in paragraphs 0014 to 0061 of JP-A No. 2006-089683 and their synthesis reaction conditions, etc., paragraphs 0008 to 0008 of JP-A-2008-248001. The compounds described in No. 0036, their synthesis reaction conditions, etc. can be referred to and are incorporated herein.

In the resin composition of the present embodiment, the content of the polymer (V) having a structural unit represented by formula (V) is 1 to 70 parts by mass based on 100 parts by mass of resin solid content in the resin composition. It is preferable that
The lower limit of the content of the polymer (V) having a structural unit represented by formula (V) is more preferably 5 parts by mass or more based on 100 parts by mass of resin solid content in the resin composition, It is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, it may be 20 parts by mass or more, and it may be 25 parts by mass or more. By setting the content of the polymer (V) having the structural unit represented by the formula (V) to the above lower limit or more, low dielectric properties, particularly low dielectric constant, can be effectively achieved. On the other hand, the upper limit of the content of the polymer (V) having a structural unit represented by formula (V) is preferably 60 parts by mass or less based on 100 parts by mass of resin solid content in the resin composition. It is preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and may be 35 parts by mass or less, or 30 parts by mass or less. By controlling the content of the polymer (V) having the structural unit represented by the formula (V) to be equal to or less than the upper limit value, the metal foil peel strength of the obtained cured product can be effectively increased.
The resin composition may contain only one type of polymer (V) having a structural unit represented by formula (V), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Further, the resin composition in this embodiment can also be configured to substantially not contain the polymer (V) having the structural unit represented by formula (V). "Substantially free" means that the content of the polymer (V) having the structural unit represented by formula (V) is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably less than 0.01 parts by mass, and may even be less than 0.001 parts by mass.

<<Cyanate ester compound>>
The resin composition of this embodiment preferably contains a cyanate ester compound. In the present embodiment, even when using a thermosetting compound such as a cyanate ester compound, which has a particularly low Df and is easily affected by ultraviolet absorbers and non-metallic organic dyes, the decrease in Df can be effectively suppressed. can.
The cyanate ester compound has one or more cyanate groups (cyanato groups) in one molecule (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably is not particularly limited as long as it is a compound containing 2), and a wide range of compounds commonly used in the field of printed wiring boards can be used. Further, the cyanate ester compound is preferably a compound in which a cyanate group is directly bonded to an aromatic skeleton (aromatic ring).
Examples of cyanate ester compounds include phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanate), naphthylene ether type cyanate ester compounds, biphenylaralkyl type cyanate ester compounds, and xylene resins. Consists of type cyanate ester compound, trisphenolmethane type cyanate ester compound, adamantane skeleton type cyanate ester compound, bisphenol M type cyanate ester compound, bisphenol A type cyanate ester compound, and diallylbisphenol A type cyanate ester compound At least one selected from the group. Among these, from the viewpoint of further improving the low water absorption of the obtained cured product, phenol novolak type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds are used. It is preferably at least one selected from the group consisting of ester compounds, bisphenol M-type cyanate ester compounds, bisphenol A-type cyanate ester compounds, and diallylbisphenol A-type cyanate ester compounds, and naphthol aralkyl-type cyanate esters. More preferably, it is a compound. These cyanate ester compounds may be prepared by known methods, or commercially available products may be used. Note that cyanate ester compounds having a naphthol aralkyl skeleton, naphthylene ether skeleton, xylene skeleton, trisphenolmethane skeleton, or adamantane skeleton have a relatively large number of functional group equivalents, and the number of unreacted cyanate ester groups is small. Therefore, cured products of resin compositions using these materials tend to have even better low water absorption. Moreover, mainly due to having an aromatic skeleton or an adamantane skeleton, plating adhesion tends to be further improved.

The resin composition of the present embodiment preferably contains a cyanate ester compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a cyanate ester compound, the lower limit of its content is preferably 0.1 parts by mass or more based on 100 parts by mass of resin solids in the resin composition. , more preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. When the content of the cyanate ester compound is 0.1 parts by mass or more, the heat resistance, flame resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulation properties of the obtained cured product are improved. There is a tendency. When the resin composition of this embodiment contains a cyanate ester compound, the upper limit of the content of the cyanate ester compound may be 70 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.
The resin composition in this embodiment may contain only one type of cyanate ester compound, or may contain two or more types of cyanate ester compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

The content (total amount) of the thermosetting compound in the resin composition of the present embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the resin solid content. It is more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more. By setting it to the above lower limit or more, heat resistance, plating adhesion, low thermal expansion, etc. tend to be further improved. Further, the upper limit of the content of the thermosetting compound is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and 80 parts by mass or less based on 100 parts by mass of the resin solid content. More preferably, the amount may be 70 parts by mass or less.
The resin composition of this embodiment may contain only one type of thermosetting compound, or may contain two or more types of thermosetting compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

<Ultraviolet absorber>
It is preferable that the resin composition of this embodiment contains an ultraviolet absorber. By including the ultraviolet absorber, transmission of i-line (wavelength: 365 nm) and h-line (wavelength: 405 nm) can be effectively suppressed.
An example of the ultraviolet absorber used in this embodiment is an ultraviolet absorber that has a maximum absorption (peak) in a wavelength range of 365 nm ± 20 nm and has a half-value width of the maximum absorption (peak) of 50 nm or more. . By using an ultraviolet absorbent having such a wide half-width width, absorption of H-line (wavelength 405 nm) tends to be effectively suppressed, which is preferable.
The type of UV absorber is not specifically defined, but examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic iminoester UV absorbers, and cyanoacrylate UV absorbers. Examples of UV absorbers include conjugated diene UV absorbers, methyldibenzoyl UV absorbers, coumarin UV absorbers, salicylate UV absorbers, acrylonitrile UV absorbers, and benzodithiazole UV absorbers. UV absorbers are preferred.

Examples of benzotriazole ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy- 3,5-Dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1 , 3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy -5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2 '-methylenebis(4-cumyl-6-benzotriazolphenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4 , 5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and the like.

Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-hydroxy-4-benzophenone. Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride dolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone , 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2- Examples include methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-bis( Examples include 2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol.

As the cyclic iminoester ultraviolet absorber, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) , 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazin-4-one) ), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1- benzoxazin-4-one) and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).

As the cyanoacrylate ultraviolet absorber, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenyl) Examples include acryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

Examples of coumarin-based ultraviolet absorbers include 7-(diethylamino)coumarin, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), ketocoumarin, and carbonylbiscoumarin.

In addition to the above, the descriptions in paragraphs 0065 to 0077 of JP-A No. 2022-000700 and the descriptions in paragraphs 0019 to 0032 of JP-A-2020-189783 can be referred to, and the contents thereof are incorporated into the present specification.

When the resin composition of the present embodiment contains an ultraviolet absorber, the content thereof is preferably more than 0 parts by mass, more preferably 0.1 parts by mass or more, based on 100 parts by mass of resin solids. It is preferably at least 0.2 parts by mass, even more preferably at least 0.3 parts by mass, even more preferably at least 0.4 parts by mass. By making it equal to or more than the lower limit, the transmittance of i-line (wavelength: 365 nm) and further h-line (wavelength: 405 nm) can be lowered, and back exposure tends to be suppressed more effectively. Further, the content of the ultraviolet absorber is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and 2.0 parts by mass or less based on 100 parts by mass of the resin solid content. It is more preferably 1.5 parts by mass or less, even more preferably 1.0 parts by mass or less, and even more preferably 0.8 parts by mass or less. By setting it below the upper limit, the dielectric loss tangent of the obtained cured product tends to be lower.
The resin composition of this embodiment may contain only one type of ultraviolet absorber, or may contain two or more types of ultraviolet absorbers. When two or more types are included, it is preferable that the total amount falls within the above range.

<Nonmetallic organic dye>
The resin composition of this embodiment preferably contains a nonmetallic organic dye. By including the non-metallic organic dye, transmission of mainly g-line (wavelength 436 nm) light can be effectively suppressed.
The nonmetallic organic dye used in this embodiment may be a dye or a pigment, but preferably contains a dye.
The non-metallic organic dye used in this embodiment is preferably a dye having maximum absorption (peak) in the wavelength range of 400 to 500 nm, and preferably a dye having maximum absorption (peak) in the wavelength range of 436 nm ± 30 nm. is even more preferable.
Further, an example of a non-metallic organic dye used in this embodiment is a dye that has a maximum absorption (peak) in a wavelength region of 436 nm±30 nm and has a half-value width of the maximum absorption (peak) of 50 nm or more. It will be done. By using a non-metallic organic dye with such a wide half-value width, absorption of the h-line (wavelength 405 nm) tends to be effectively suppressed, which is preferable.
The color of the nonmetallic organic dye is not particularly limited, but from the viewpoint of design, it is preferable to use one that appears black to the human eye.

Examples of nonmetallic organic dyes include cyanine dyes, triphenylmethane dyes, anthraquinone dyes, xanthene dyes, azo dyes, benzopyran dyes, indigo dyes, quinoline dyes, perinone dyes, and perylene dyes, and anthraquinone dyes and/or perinone dyes. Dyes are preferred. For details of these non-metallic organic dyes, the description in JP-A-02-089683 and the description in paragraph 0031 of JP-A-2011-102384 can be referred to, and the contents thereof are incorporated into the present specification.

When the resin composition of the present embodiment contains a nonmetallic organic dye, the content thereof is preferably more than 0 parts by mass, and preferably 0.2 parts by mass or more, based on 100 parts by mass of the resin solid content. It is more preferably 0.3 parts by mass or more, even more preferably 0.4 parts by mass or more, and even more preferably 0.45 parts by mass or more. By setting it above the lower limit, the transmittance of the g-line (wavelength: 436 nm) and even the h-line (wavelength: 405 nm) can be lowered, and back exposure tends to be suppressed more effectively. Further, the content of the nonmetallic organic dye is preferably 2.0 parts by mass or less, more preferably 1.75 parts by mass or less, and 1.5 parts by mass based on 100 parts by mass of the resin solid content. It is more preferably at most 1.25 parts by mass, even more preferably at most 1.0 parts by mass. By setting it below the above upper limit, the dielectric loss tangent of the obtained cured product can be lowered, and the glass transition temperature tends to be further improved.
The resin composition of this embodiment may contain only one type of nonmetallic organic dye, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Furthermore, in this embodiment, the mass ratio of the ultraviolet absorber to the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is preferably 0.15 or more and 4.0 or less. is preferred. By setting such a ratio, it is possible to more effectively lower the transmittance of G-line (wavelength 436 nm), H-line (wavelength 405 nm), and I-line (wavelength 365 nm), and more effectively reduce back exposure. can be suppressed. In particular, ultraviolet absorbers and nonmetallic organic dyes tend to lower the glass transition temperature of cured products obtained from resin compositions, but in this embodiment, the ultraviolet absorbers and nonmetallic organic dyes are used together. Accordingly, the content of these components in the resin composition can be relatively reduced, and a decrease in the glass transition temperature can be effectively suppressed.
The mass ratio of the ultraviolet absorber to the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is more preferably 0.2 or more, even more preferably 0.3 or more, and even more preferably 0.4 or more. There may be. Furthermore, the mass ratio of the ultraviolet absorber to the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is more preferably 3.0 or less, even more preferably 1.5 or less, and 1.3 It is more preferably below, even more preferably 1.2 or less, even more preferably 1.1 or less.

When the resin composition of the present embodiment contains an ultraviolet absorber and a nonmetallic organic dye, the total content of the ultraviolet absorber and the nonmetallic organic dye should be more than 0 parts by mass based on 100 parts by mass of the resin solid content. is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more, even more preferably 0.6 parts by mass or more, and even more preferably 0.8 parts by mass or more. It is even more preferable. By setting the above lower limit value or more, the transmittance of the g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), and i-line (wavelength: 365 nm) can be lowered, and back exposure tends to be further suppressed. Further, the total content of the ultraviolet absorber and the nonmetallic organic dye is preferably 4.5 parts by mass or less, more preferably 4.0 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and even more preferably 1.75 parts by mass or less. By setting it below the above upper limit, the dielectric loss tangent of the obtained cured product can be lowered, and the glass transition temperature tends to be further improved.

The resin composition of the present embodiment can be configured to be substantially free of carbon black and further, conductive substances. Substantially free of carbon black or conductive substances means that the content of carbon black (furthermore, conductive substances) is 10% by mass of the content of nonmetallic organic dyes contained in the resin composition. It is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. With such a configuration, the insulation properties of the resulting resin composition or cured product can be made higher.

<Filling material>
The resin composition of this embodiment preferably contains a filler. By including the filler, physical properties such as dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, and low thermal expansion of the resin composition and its cured product can be further improved.
Moreover, it is more preferable that the filler used in this embodiment has excellent low dielectric properties (low Dk and/or low Df). For example, the filler used in this embodiment preferably has a dielectric constant (Dk) of 8.0 or less, more preferably 6.0 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method, More preferably, it is 4.0 or less. Moreover, the lower limit of the relative permittivity is practically, for example, 2.0 or more. Furthermore, the filler used in this embodiment preferably has a dielectric loss tangent (Df) of 0.05 or less, more preferably 0.01 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method. Further, the lower limit value of the dielectric loss tangent is practically, for example, 0.0001 or more.

The type of filler used in this embodiment is not particularly limited, and those commonly used in the industry can be suitably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica, metal oxides such as alumina, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide. , complex oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, calcium titanate, nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, aluminum hydroxide, Heat-treated aluminum hydroxide products (aluminum hydroxide heat-treated to reduce some of the crystal water), metal hydroxides (including hydrates) such as boehmite and magnesium hydroxide, molybdenum oxide and molybdic acid Molybdenum compounds such as zinc, barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, Inorganic fillers such as S-glass, M-glass G20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass ( Inorganic fillers), styrene type, butadiene type, acrylic type rubber powder, core shell type rubber powder, silicone resin powder, silicone rubber powder, silicone composite powder, polytetrafluoroethylene (PTFE) filler, tetrafluoroethylene -Perfluoroalkyl vinyl ether copolymer (PFA) filler, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) filler, tetrafluoroethylene-ethylene copolymer (ETFE) filler, polychlorotrifluoroethylene (PCTFE) filler Examples include organic fillers (organic fillers) such as fluororesin fillers.
In this embodiment, the filler preferably includes an inorganic filler and/or a fluororesin filler. The inorganic filler includes one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. is preferable, and from the viewpoint of low dielectric properties (low Dk and/or low Df), it is more preferable to contain one or more selected from the group consisting of silica and aluminum hydroxide, and it is even more preferable to contain silica. . As a fluororesin filler. It is more preferable to include one or more types selected from the group consisting of polytetrafluoroethylene (PTFE) filler and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) filler. By using these inorganic fillers and fluororesin fillers, properties such as heat resistance, dielectric properties, thermal expansion properties, dimensional stability, and flame retardance of the cured product of the resin composition are further improved.

The content of the filler in the resin composition of the present embodiment can be appropriately set depending on the desired characteristics, and is not particularly limited, but is 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. It is preferably at least 20 parts by mass, more preferably at least 40 parts by mass, even more preferably at least 60 parts by mass, even more preferably at least 80 parts by mass. preferable. By setting it to the above lower limit or more, low thermal expansion property and low dielectric loss tangent property tend to be further improved. Further, the upper limit value of the filler content is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and preferably 500 parts by mass or less based on 100 parts by mass of the resin solid content. It is more preferably 300 parts by mass or less, even more preferably 250 parts by mass or less, and may be 200 parts by mass or less, or 150 parts by mass or less. By setting it below the upper limit value, moldability tends to be further improved.
In the resin composition of the present embodiment, as an example of a preferable embodiment, the content of the filler is 1 to 95% by mass of the components excluding the solvent, and the content of the filler is 30% to 80% by mass. Illustrated.
The resin composition of this embodiment may contain only one type of filler, or may contain two or more types of filler. When two or more types are included, it is preferable that the total amount falls within the above range.

<Low molecular vinyl compound with a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule>
The resin composition of the present embodiment is a low-molecular vinyl compound (hereinafter simply referred to as a "low-molecular vinyl compound") having a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule. ) may also be included. By blending a low molecular weight vinyl compound, the moisture absorption and heat resistance of the resulting cured product tends to be further improved.
Here, the carbon-carbon unsaturated bonds constituting the organic group containing carbon-carbon unsaturated bonds do not include those included as part of an aromatic ring. On the other hand, it is meant to include carbon-carbon unsaturated bonds included as part of non-aromatic rings. An example of a carbon-carbon unsaturated bond included as part of the non-aromatic ring includes a cyclohexenyl group. It is also intended to include portions other than the terminals of linear or branched organic groups, ie, carbon-carbon unsaturated bonds (eg, vinylene groups) contained in the linear or branched chains.
In this embodiment, the organic group containing the carbon-carbon unsaturated bond preferably has a structure of CH ₂ =C(X)- (X is a hydrogen atom or a methyl group). In this way, by employing a compound containing a carbon-carbon unsaturated bond at the end of the molecule, it is possible to more effectively interact with the vinyl group of the polymer (V) having the structural unit represented by formula (V). It becomes possible to react.
The organic group containing a carbon-carbon unsaturated bond is more preferably one selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acrylic group, and more preferably a vinyl group. preferable.

The low molecular weight vinyl compound used in this embodiment is preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and silicon atoms. More preferably, it is composed only of atoms selected from the group consisting of atoms, oxygen atoms, and silicon atoms, and it is composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms. It is even more preferable.
The low molecular weight vinyl compound used in this embodiment may or may not have a polar group. It is preferable that the low molecular weight vinyl compound used in this embodiment has no polar group. Examples of the polar group include an amino group, a carboxyl group, a hydroxy group, and a nitro group.

In this embodiment, the molecular weight of the low molecular weight vinyl compound is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more. By setting it to the above-mentioned lower limit or more, there is a tendency that volatilization of the low molecular weight vinyl compound from the resin composition of this embodiment, its cured product, etc. can be suppressed. The upper limit of the molecular weight of the low molecular weight vinyl compound is preferably 500 or less, more preferably 400 or less, even more preferably 300 or less, even more preferably 200 or less, and 150 or less. Good too. By setting it below the above-mentioned upper limit, the effect of increasing the reactivity with the polymer (V) having the structural unit represented by the formula (V) tends to be further improved.
When the resin composition of this embodiment contains two or more types of low molecular weight vinyl compounds, it is preferable that the average molecular weight value of the low molecular weight vinyl compounds is within the above range, and the molecular weight of each compound is within the above preferable range. is more preferable.

In this embodiment, the low molecular weight vinyl compound preferably has a boiling point of 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. By setting the value above the lower limit, volatilization of the low molecular weight vinyl compound during thermosetting of the resin composition is suppressed, and the polymer (V) having the structural unit represented by the formula (V) is more effectively produced. It is possible to react the vinyl group possessed by a low-molecular-weight vinyl compound. The boiling point of the low molecular weight vinyl compound is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. By controlling the amount to be less than or equal to the upper limit, it is possible to make it difficult for residual solvent to remain in the cured product.
When the resin composition of the present embodiment contains two or more types of low-molecular vinyl compounds, it is sufficient that the average boiling point falls within the above-mentioned range, but it is preferable that the boiling point of each compound falls within the above-mentioned preferred range.

Examples of low-molecular vinyl compounds include (meth)acrylic acid ester compounds, aromatic vinyl compounds (preferably styrene compounds), saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, and ethylenically unsaturated carboxylic acids. Anhydrides, ethylenically unsaturated dicarboxylic acid monoalkyl esters, ethylenically unsaturated carboxylic acid amides, vinyl silane compounds (e.g., vinyltrialkoxysilanes, etc.), acrylic silane compounds (e.g., acrylic trialkoxysilanes, etc.), methacrylic silane compounds (for example, methacryltrialkoxysilane, etc.), styrylsilane compounds (for example, styryltrialkoxysilane, etc.), and the like.
The first forms of low-molecular vinyl compounds include (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, It is at least one selected from the group consisting of ethylenically unsaturated dicarboxylic acid monoalkyl esters and ethylenically unsaturated carboxylic acid amides.
The second form of the low molecular weight vinyl compound is selected from the group consisting of (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl silane compounds, acrylic silane compounds, methacrylic silane compounds, and styryl silane compounds. It is at least one kind, and aromatic vinyl compounds and/or vinyl silane compounds are preferred.
Specific examples of low molecular weight vinyl compounds include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane, and vinyltriethoxysilane.

In the resin composition of the present embodiment, the content of the low molecular weight vinyl compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the resin solid content. More preferably, the amount is 5 parts by mass or more. By setting the amount to be equal to or more than the lower limit, the amount of unreacted functional groups in the obtained cured product tends to decrease, and the moisture absorption and heat resistance tends to improve. Further, the upper limit of the content of the low molecular weight vinyl compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and 10 parts by mass or less, based on 100 parts by mass of the resin solid content. The amount is more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less. By setting it below the above-mentioned upper limit, the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of low-molecular-weight vinyl compound, or may contain two or more types of low-molecular-weight vinyl compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

<Aromatic oligomer>
The resin composition of this embodiment may contain an aromatic oligomer. The aromatic oligomer is an oligomer having a structural unit derived from an aromatic vinyl compound, and usually refers to a compound having a weight average molecular weight of less than 3,000. Aromatic oligomers are also usually thermoplastic oligomers. Note that the aromatic oligomer in this embodiment does not include a polymer or elastomer having a structural unit represented by formula (V).
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, and 4-methylstyrene. -Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2 -vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene and divinylbenzene. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferred, and α-methylstyrene is more preferred.

The aromatic oligomer may contain structural units derived from monomers other than aromatic vinyl compounds. Such other monomers include (meth)acrylic acid, (meth)acrylic acid derivatives, (meth)acrylamide, (meth)acrylamide derivatives, (meth)acrylonitrile, isoprene, 1,3-butadiene, ethylene, vinyl acetate. , vinyl chloride, vinylidene chloride, N-vinylindole, N-vinylphthalimide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylcaprolactam and the like.

The content of the structural unit derived from the aromatic vinyl compound in the aromatic oligomer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, even more preferably 90% by mass or more, and 95% by mass or more. It is even more preferable that the amount is % by mass or more.

The weight average molecular weight (Mw) of the aromatic oligomer is preferably 300 or more, more preferably 500 or more, even more preferably 1,000 or more, and usually less than 3,000. , is preferably 2,800 or less, more preferably 2,500 or less, and may be 2,000 or less. The weight average molecular weight (Mw) of the aromatic oligomer is a value determined in terms of standard polystyrene by gel permeation chromatography.

Examples of aromatic oligomers include polystyrene, polyα-methylstyrene, poly4-methylstyrene, styrene/α-methylstyrene copolymer, styrene/4-methylstyrene copolymer, α-methylstyrene/4-methylstyrene. copolymers, and styrene/α-methylstyrene/4-methylstyrene copolymers. In addition, one type of aromatic oligomer may be used alone, or two or more types may be used in combination.

Commercially available products may be used as the aromatic oligomer. Commercially available aromatic oligomers include, for example, Picolastic A5 (polystyrene, softening point 5°C, Mw 350), Picolastic A-75 (polystyrene, softening point 74°C, Mw 1300), Picotex 75 (α-methylstyrene/ 4-methylstyrene copolymer, softening point 75°C, Mw 1100), Picotex LC (α-methylstyrene/4-methylstyrene copolymer, softening point 91°C, Mw 1350), Crystallex 3070 (styrene/α-methyl Styrene copolymer, softening point 70°C, Mw 950), Crystallex 3085 (styrene/α-methylstyrene copolymer, softening point 85°C, Mw 1150), Crystallex 3100 (styrene/α-methylstyrene copolymer, softening YS Resin SX-100 (polystyrene, softening point 100°C, Mw 2500; manufactured by Yasuhara Chemical Co., Ltd.), FMR-0150 (styrene/aromatic hydrocarbon copolymer) Polymer, softening point 145°C, Mw 2040; manufactured by Mitsui Chemicals), FTR-6100 (styrene/aliphatic hydrocarbon copolymer, softening point 95°C, Mw 1210; manufactured by Mitsui Chemicals), FTR-6110 (styrene/ Aliphatic hydrocarbon copolymer, softening point 110°C, Mw 1570; manufactured by Mitsui Chemicals), FTR-6125 (styrene/aliphatic hydrocarbon copolymer, softening point 125°C, Mw 1950; manufactured by Mitsui Chemicals), FTR-7100 (styrene/α-methylstyrene/aliphatic hydrocarbon copolymer, softening point 100°C, Mw 1440; manufactured by Mitsui Chemicals), FTR-0100 (poly α-methylstyrene, softening point 100°C, Mw 1960; (manufactured by Mitsui Chemicals), FTR-2120 (styrene/α-methylstyrene copolymer, softening point 120°C, Mw 2630; manufactured by Mitsui Chemicals), and the like.

When the resin composition of the present embodiment contains an aromatic oligomer, the content thereof is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the resin solid content. It is more preferably 3 parts by mass or more, and may be 4 parts by mass or more. By making it equal to or more than the lower limit value, the dielectric constant and the dielectric loss tangent tend to be lower. Further, the upper limit of the aromatic oligomer content is preferably 45 parts by mass or less, more preferably 30 parts by mass or less, and 15 parts by mass or less based on 100 parts by mass of the resin solid content. is more preferable, even more preferably 10 parts by mass or less, and may be 8 parts by mass or less. By setting it below the upper limit value, chemical resistance tends to be further improved.
The resin composition of this embodiment may contain only one type of aromatic oligomer, or may contain two or more types of aromatic oligomers. When two or more types are included, it is preferable that the total amount falls within the above range.

<<Elastomer>>
The resin composition of this embodiment may contain an elastomer. The elastomer may be thermoplastic, thermosetting, or neither thermoplastic nor thermosetting, but thermoplastic is preferred.
The elastomer in this embodiment is not particularly limited, and examples thereof include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, and styrene. At least one selected from the group consisting of ethylene propylene styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof can be mentioned.
Further, examples of the elastomer include oligomers or polymers having a curable vinyl functional group, and polybutadiene resins described in paragraphs 0044 and 0045 of JP-A No. 2019-194312, the contents of which are incorporated herein.

The number average molecular weight of the elastomer (preferably a thermoplastic elastomer) used in this embodiment is preferably 1000 or more. By setting the number average molecular weight of the elastomer to 1000 or more, the resulting cured product tends to have better low dielectric properties (Dk and/or Df, particularly low dielectric loss tangent). The number average molecular weight is preferably 1500 or more, more preferably 2000 or more, and may be 50,000 or more, 60,000 or more, 70,000 or more, or 80,000 or more depending on the application. Good too. The upper limit of the number average molecular weight of the elastomer is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By controlling the number average molecular weight of the elastomer to be less than or equal to the above upper limit, the solubility of the elastomer component in the resin composition tends to improve.
When the resin composition of this embodiment contains two or more types of elastomers, it is preferable that the number average molecular weight of the mixture satisfies the above range.

The elastomer used in this embodiment includes a resin containing a polybutadiene structure. Part or all of the polybutadiene structure may be hydrogenated. Specific examples include Nippon Soda Co., Ltd., B-1000, B-2000, B-3000, BI-2000, BI-3000, CRAY VALLEY, Ricon100, Ricon130, Ricon131, Ricon142, Ricon150, Ricon181, Ricon 184th grade can be mentioned.

The elastomer used in this embodiment includes a resin containing a poly(meth)acrylate structure. Specific examples include Teisan Resin manufactured by Nagase ChemteX, ME-2000, W-197C, KG-15, and KG-3000 manufactured by Negami Kogyo.

Examples of the elastomer used in this embodiment include resins containing a polycarbonate structure. A resin containing a polycarbonate structure is sometimes referred to as a "polycarbonate resin." Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxy groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxy groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, and urethane group-containing carbonate resins. Examples include carbonate resins containing carbonate resins, carbonate resins containing epoxy groups, and the like. Here, the reactive group refers to a functional group that can react with other components, such as a hydroxy group, a phenolic hydroxyl group, a carboxy group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.
Specific examples of the polycarbonate resin include FPC0220 and FPC2136 manufactured by Mitsubishi Gas Chemical Co., Ltd., and T6002 and T6001 (polycarbonate diol) manufactured by Asahi Kasei Chemicals.

The elastomer used in this embodiment includes a resin containing a polysiloxane structure. Specific examples include SMP-2006, SMP-2003PGMEA, SMP-5005PGMEA, KR-510, and SMP-7014-3S manufactured by Shin-Etsu Silicone.

Examples of the elastomer used in this embodiment include resins containing a polyalkylene structure and/or a polyalkyleneoxy structure. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of resins containing a polyalkylene structure and/or polyalkyleneoxy structure include PTXG-1000 and PTXG-1800 manufactured by Asahi Kasei Fibers.

The elastomer used in this embodiment includes a resin containing a polyisoprene structure. Specific examples include KL-610 and KL613 manufactured by Kuraray.

The elastomer used in this embodiment includes a resin containing a polyisobutylene structure. Specific examples include SIBSTAR-073T (styrene-isobutylene-styrene triblock copolymer) and SIBSTAR-042D (styrene-isobutylene diblock copolymer) manufactured by Kaneka.

In this embodiment, the elastomer (preferably a thermoplastic elastomer) is preferably an elastomer containing a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "elastomer (e)"). By using such an elastomer (e), the obtained cured product has better low dielectric properties (Dk and/or Df, especially low dielectric loss tangent).

The elastomer (e) contains styrene monomer units. By including the styrene monomer unit, the solubility of the elastomer (e) in the resin composition is improved. Styrene monomers include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among these, styrene is particularly preferred.
The content of styrene monomer units in the elastomer (e) is preferably in the range of 10 to 80% by mass, more preferably in the range of 13 to 70% by mass, and more preferably in the range of 15 to 50% by mass of the total monomer units. is more preferable, and the range of 20 to 40% by mass is more preferable. If the content of styrene monomer units is 80% by mass or less, the adhesiveness and tackiness to the substrate etc. will be better. Further, if it is 10% by mass or more, it is preferable because it is possible to suppress the increase in adhesion, it is difficult to form adhesive residue or stop marks, and the easy peelability between the adhesive surfaces tends to be good.
The elastomer (e) may contain only one type of styrene monomer unit, or may contain two or more types of styrene monomer units. When two or more types are included, it is preferable that the total amount is within the above range.
For the method of measuring the content of styrene monomer units in the elastomer (e) of the present embodiment, the description in International Publication No. 2017/126469 can be referred to, and the contents thereof are incorporated herein. The same applies to the conjugated diene monomer unit, etc., which will be described later.

The elastomer (e) contains conjugated diene monomer units. By including the conjugated diene monomer unit, the solubility of the elastomer (e) in the resin composition is improved. The conjugated diene monomer is not particularly limited as long as it is a diolefin having one pair of conjugated double bonds. Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- Examples include 1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred.
The elastomer (e) may contain only one type of conjugated diene monomer unit, or may contain two or more types.

In the above elastomer (e), the mass ratio of styrene monomer units to conjugated diene monomer units is in the range of styrene monomer units/conjugated diene monomer units = 5/95 to 80/20. It is preferably in the range of 7/93 to 77/23, and even more preferably in the range of 10/90 to 70/30. If the mass ratio of the styrene polymer unit to the conjugated diene monomer unit is in the range of 5/95 to 80/20, it is possible to suppress the increase in adhesion and maintain high adhesion, and the easy peelability between adhesive surfaces is good. become.

In the above elastomer (e), all of the conjugated diene bonds of the elastomer may be hydrogenated, some of them may be hydrogenated, or there is no need to be hydrogenated.

The elastomer (e) may or may not contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit. Examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.
In the elastomer (e), the total amount of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more of the total monomer units, and 97% by mass or more. It is more preferably at least 99% by mass, even more preferably at least 99% by mass.
As described above, the elastomer (e) may contain only one type of styrene monomer unit and conjugated diene monomer unit, or may contain two or more types of each. When two or more types are included, it is preferable that the total amount falls within the above range.

The elastomer (e) used in this embodiment may be a block polymer or a random polymer. In addition, even if it is a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, an unhydrogenated elastomer in which the conjugated diene monomer unit is not hydrogenated, or a partially hydrogenated elastomer in which the conjugated diene monomer unit is partially hydrogenated, Often, unhydrogenated or partially hydrogenated elastomers are preferred.
In one embodiment of this embodiment, the elastomer (e) is a hydrogenated elastomer. Here, the hydrogenated elastomer means, for example, an elastomer in which a double bond based on a conjugated diene monomer unit is hydrogenated, and in addition to one with a hydrogenation rate (hydrogenation rate) of 100%, The purpose is to include 80% or more. The hydrogenation rate in the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. In this embodiment, the hydrogenation rate is calculated from the measurement results of ¹ H-NMR spectrum measurement.
In one embodiment of this embodiment, the elastomer (e) is an unhydrogenated elastomer. Here, unhydrogenated elastomer refers to the proportion of double bonds based on conjugated diene monomer units in the elastomer that are hydrogenated, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. say something The hydrogenation rate is preferably 15% or less, more preferably 10% or less, even more preferably 5% or less.
On the other hand, partially hydrogenated elastomer refers to an elastomer in which a portion of the double bonds based on conjugated diene monomer units are hydrogenated, and the hydrogenation rate (hydrogenation rate) is usually less than 80%. , more than 20%.

Commercial products of the elastomer (e) used in this embodiment include SEPTON (registered trademark) 2104, V9461, and S8104 manufactured by Kuraray Co., Ltd., and SEPTON (registered trademark) manufactured by Asahi Kasei Corporation. O. E. (registered trademark) S1606, S1613, S1609, S1605, H1041, H1043, P2000, MP10 of Tuftec (registered trademark) manufactured by Asahi Kasei Corporation, DYNARON (registered trademark) 9901P, TR2250 manufactured by JSR Corporation, etc. .

The elastomer used in this embodiment may also be a liquid diene. Liquid diene means a liquid elastomer containing a conjugated diene monomer unit. Conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1 , 3-pentadiene, 1,3-hexadiene, and farnesene, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred.
Examples of the liquid diene used in this embodiment include liquid polybutadiene, liquid polyisoprene, modified products of liquid polybutadiene, modified products of liquid polyisoprene, liquid acrylonitrile-butadiene copolymers, and liquid styrene-butadiene copolymers. .
Further, the number average molecular weight of the liquid diene is not particularly limited as long as it is liquid at 20°C, but is preferably 500 or more and 10,000 or less.

When the resin composition of the present embodiment contains an elastomer (preferably elastomer (e)), the content thereof is preferably 1 part by mass or more, and 2 parts by mass or more based on 100 parts by mass of the resin solid content. It is more preferable that it is, it is still more preferable that it is 3 parts by mass or more, and it may be 4 parts by mass or more. By making it equal to or more than the lower limit, the low dielectric properties (Dk and/or Df, especially low dielectric loss tangent) tend to be further improved. Further, the upper limit of the content of the elastomer is preferably 45 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, based on 100 parts by mass of the resin solid content. It is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. By setting it below the upper limit value, heat resistance tends to be further improved.
The resin composition of this embodiment may contain only one type of thermoplastic elastomer, or may contain two or more types of thermoplastic elastomer. When two or more types are included, it is preferable that the total amount falls within the above range.

<Flame retardant>
The resin composition of this embodiment may contain a flame retardant. Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, with phosphorus-based flame retardants being preferred.
Known flame retardants can be used, such as brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromo Halogen flame retardants such as toluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate , cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phosphazene, 1,3-phenylenebis(2,6-dixylenyl phosphate), 10-(2,5- Phosphorous flame retardants such as dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, inorganic types such as aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, and antimony trioxide. Examples include flame retardants, silicone-based flame retardants such as silicone rubber, and silicone resin.
In the present embodiment, among these, 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferred because it does not impair low dielectric properties.

When the resin composition of the present embodiment contains a flame retardant, the content thereof is preferably 1 part by mass or more, and preferably 5 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. is more preferable, more preferably 10 parts by mass or more, and may be 13 parts by mass or more. Further, the lower limit of the flame retardant content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and may be 20 parts by mass or less.
One kind of flame retardant can be used alone or two or more kinds can be used in combination. When two or more types are used, the total amount falls within the above range.

<Active ester compound>
The resin composition of this embodiment may contain an active ester compound to the extent that the effects of the present invention are not impaired. The active ester compound is not particularly limited, and for example, the description in paragraphs 0064 to 0066 of International Publication No. 2021/172317 can be referred to, the contents of which are incorporated herein.

When the resin composition of this embodiment contains an active ester compound, it is preferably 1 part by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition. .
The resin composition in this embodiment may contain only one type of active ester compound, or may contain two or more types of active ester compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain an active ester compound. "Substantially free" means that the content of the active ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, per 100 parts by mass of resin solids in the resin composition. More preferably, it is less than 0.01 part by mass.

<Silane coupling agent>
The resin composition of this embodiment may further contain a silane coupling agent. By containing the silane coupling agent, the resin composition of this embodiment further improves the dispersibility of the filler and increases the adhesive strength between the components of the resin composition of this embodiment and the base material described below. There is a tendency for further improvement.

Silane coupling agents are not particularly limited, and include silane coupling agents that are generally used for surface treatment of inorganic materials, such as aminosilane compounds (for example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl) -γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (eg, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, and the like. Among these, the silane coupling agent is preferably an epoxysilane compound. Examples of the epoxysilane compound include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

When the resin composition of the present embodiment contains a silane coupling agent, the content thereof is preferably 0.1 parts by mass or more, and preferably 0.5 parts by mass or more based on 100 parts by mass of resin solid content. It is more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, and even more preferably 2.5 parts by mass or more. By setting it to the above lower limit or more, the dispersibility of the inorganic filler tends to be further improved. Further, the upper limit of the content of the silane coupling agent is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferably 0 parts by mass or less, even more preferably 4.0 parts by mass or less. When the content is below the upper limit, chemical resistance and heat resistance tend to be further improved.
The resin composition of this embodiment may contain only one type of silane coupling agent, or may contain two or more types of silane coupling agents. When two or more types are included, it is preferable that the total amount falls within the above range.

<Dispersant>
The resin composition of this embodiment may contain a dispersant. As the dispersant, those commonly used for paints can be suitably used, and the type thereof is not particularly limited. As the dispersant, preferably a copolymer-based wetting and dispersing agent is used, and specific examples thereof include DISPERBYK®-110, 111, 161, 180, 2009, and 2152 manufactured by BYK Chemie Japan Co., Ltd. , 2155, BYK (registered trademark)-W996, W9010, W903, W940, etc.

When the resin composition of the present embodiment contains a dispersant, the lower limit of its content is preferably 0.01 parts by mass or more, and 0.01 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferably 1 part by mass or more, and may be 0.3 part by mass or more. Further, the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass based on 100 parts by mass of resin solids in the resin composition. The following may be sufficient.
One type of dispersant can be used alone or two or more types can be used in combination. When two or more types are used, the total amount falls within the above range.

<Curing accelerator>
The resin composition of this embodiment may further contain a curing accelerator. Examples of the curing accelerator include, but are not limited to, imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di- tert-butyl-di-perphthalate, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl- Organic peroxides such as 2,5-bis(t-butylperoxy)hexyne-3; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine , 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine and other tertiary amines; phenol , xylenol, cresol, resorcin, catechol, and other phenols; high-temperature decomposition type radical generators such as 2,3-dimethyl-2,3-diphenylbutane; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, Organic metal salts such as manganese octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; These organic metal salts are dissolved in hydroxyl group-containing compounds such as phenol and bisphenol; tin chloride , inorganic metal salts such as zinc chloride and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyltins, and alkyltin oxides.
Preferred curing accelerators are imidazoles and organometallic salts, and it is more preferred to use both imidazoles and organometallic salts in combination.

When the resin composition of the present embodiment contains a curing accelerator, the lower limit of its content is preferably 0.005 parts by mass or more with respect to 100 parts by mass of resin solids in the resin composition, and 0. It is more preferably .01 part by mass or more, and even more preferably 0.1 part by mass or more. Further, the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 2 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is less than 1 part.
The curing accelerator can be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

<Solvent>
The resin composition of this embodiment may contain a solvent, and preferably contains an organic solvent. When containing a solvent, the resin composition of the present embodiment is in a form (solution or varnish) in which at least a portion, preferably all, of the various resin solid components described above are dissolved or compatible with the solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve or be compatible with at least a portion, preferably all, of the various resin solids mentioned above. Examples of the polar organic solvent include ketones, etc. (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetic acid) isoamyl, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamide, etc.), and nonpolar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).
One kind of solvent can be used alone or two or more kinds can be used in combination. When two or more types are used, the total amount falls within the above range.

<Other ingredients>
The resin composition of this embodiment may contain various polymeric compounds such as thermoplastic resins and oligomers thereof, and various additives in addition to the above-mentioned components. Examples of additives include antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, thickeners, flow regulators, lubricants, antifoaming agents, leveling agents, brightening agents, polymerization inhibitors, etc. It will be done. These additives can be used alone or in combination of two or more.

<Method for manufacturing resin composition>
The method for producing the resin composition of the present embodiment is not particularly limited, but includes, for example, a method in which each component is sequentially blended into a solvent and thoroughly stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading treatments can be performed. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersion treatment using a stirring tank equipped with a stirrer having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading processes can be appropriately performed using, for example, a device for mixing such as a ball mill or a bead mill, or a known device such as a revolving or autorotating type mixing device.

<Application>
The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of the present embodiment can be used as a low thermal expansion coefficient material, a high relative permittivity material, a low relative permittivity material, or a low dielectric loss tangent material for forming an insulating layer such as an insulating layer of a printed wiring board. It can be suitably used as a resin composition and a resin composition for electronic materials such as semiconductor packages. Among them, as a low dielectric constant material and/or a low dielectric loss tangent material, it is more suitably used as a resin composition for forming an insulating layer such as an insulating layer of a printed wiring board, and a resin composition for electronic materials such as semiconductor packages. be able to. The resin composition of this embodiment can be suitably used as a material for prepreg, a metal foil-clad laminate using prepreg, a resin composite sheet, and a printed wiring board.

The resin composition of this embodiment preferably has a low dielectric loss tangent (Df) when cured. Specifically, the dielectric loss tangent (Df) at 10 GHz measured according to the cavity resonator perturbation method is preferably less than 0.0028, more preferably less than 0.0027, and preferably less than 0.0026. More preferred. Although the lower limit of the dielectric loss tangent (Df) is not particularly determined, for example, 0.0001 or more is practical.
The resin composition of the present embodiment also preferably has a low dielectric constant (Dk) when cured. Specifically, it is preferable that the dielectric constant (Dk) at 10 GHz measured according to the cavity resonator perturbation method is 3.0 or less. Although the lower limit of the dielectric constant (Dk) is not particularly determined, for example, 0.01 or more is practical.
Such low dielectric properties are achieved by using a thermosetting compound having low dielectric properties and by precisely adjusting the amounts of the ultraviolet absorber and nonmetallic organic dye in the resin composition.
More specifically, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product are measured by the method described in the Examples described below.

The cured product of the resin composition of this embodiment preferably has a glass transition temperature (Tan δ) according to DMA (dynamic mechanical measurement) of 245°C or higher, more preferably 255°C or higher. Such a high glass transition temperature is achieved by reducing the content of the ultraviolet absorber and non-metallic organic dye in the resin composition. Although the upper limit of the glass transition temperature is not particularly determined, for example, 350° C. or lower is practical.
More specifically, the glass transition temperature (Tan δ) is measured by the method described in the Examples below.

The resin composition of the present embodiment is suitably used as a layered (including film-like, sheet-like, etc.) material such as prepreg, resin composite sheet, etc., which becomes an insulating layer of a printed wiring board. The thickness of the layered material is preferably 0.1 μm or more. The upper limit of the thickness may be 200 μm or less and 180 μm or less, but the present invention is also applicable to thin film materials of 100 μm or less, 80 μm or less, 50 μm or less, 30 μm or less, and 15 μm or less. High value. Incidentally, the thickness of the above-mentioned layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like.
The material formed from the resin composition of this embodiment may be used for forming a pattern by exposure and development, or may be used for applications that are not exposed and developed. It is particularly suitable for applications that do not require exposure and development.

<<Prepreg>>
The prepreg of this embodiment is formed from a base material (prepreg base material) and the resin composition of this embodiment. The prepreg of the present embodiment can be produced by, for example, applying the resin composition of the present embodiment to a base material (for example, impregnating and/or coating it), and then heating it (for example, drying it at 120 to 220°C for 2 to 15 minutes). etc.) by semi-curing. In this case, the amount of the resin composition adhered to the base material, that is, the amount of the resin composition (including filler) relative to the total amount of prepreg after semi-curing, is preferably in the range of 20 to 99% by mass, and 20 to 80% by mass. % range is more preferable.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. Examples of the material of the base material include glass fiber (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.) , inorganic fibers other than glass (eg, quartz, etc.), and organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like. These base materials may be used alone or in combination of two or more. Among these base materials, from the viewpoint of dimensional stability, woven fabrics subjected to ultra-opening treatment and packing treatment are preferable, and from the viewpoints of strength and low water absorption, the base material has a thickness of 200 μm or less, a mass of 250 g/ A glass woven fabric having a size of m ² or less is preferable, and from the viewpoint of moisture absorption and heat resistance, a glass woven fabric surface-treated with a silane coupling agent such as epoxy silane or amino silane is preferable. From the viewpoint of electrical properties, a low dielectric glass cloth made of glass fibers exhibiting a low dielectric constant and a low dielectric loss tangent, such as L-glass, NE-glass, and Q-glass, is more preferable.
Examples of the base material having a low dielectric constant include a base material having a dielectric constant of 5.0 or less (preferably 3.0 to 4.9). Examples of the low dielectric loss tangent base material include base materials with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative permittivity and dielectric loss tangent are values measured at a frequency of 10 GHz using a perturbation method cavity resonator.

<<Metal foil clad laminate>>
The metal foil-clad laminate of the present embodiment includes a layer formed from the resin composition of the present embodiment and/or a layer formed from the prepreg of the present embodiment, and a layer formed from the resin composition of the present embodiment, and a layer formed from the prepreg of the present embodiment, and a layer formed from the resin composition of the present embodiment, and a layer formed from the prepreg of the present embodiment, and Including metal foil. As a method for producing the metal foil-clad laminate of this embodiment, for example, at least one prepreg of this embodiment is arranged (preferably two or more prepregs are stacked), metal foil is arranged on one or both sides of the prepreg, and laminated molding is performed. One method is to do so. More specifically, it can be produced by arranging a metal foil such as copper or aluminum on one or both sides of a prepreg and laminating it. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited, and may be about 1.5 to 70 μm. Further, when copper foil is used as the metal foil, it is preferable that the roughness Rz of the surface of the copper foil measured according to JIS B0601:2013 is adjusted to 0.2 to 4.0 μm. By setting the roughness Rz of the copper foil surface to 0.2 μm or more, the roughness of the copper foil surface becomes appropriate, and the copper foil peel strength tends to be further improved. On the other hand, by setting the roughness Rz of the copper foil surface to 4.0 μm or less, the roughness of the copper foil surface becomes appropriate, and the dielectric loss tangent characteristics of the obtained cured product tend to be further improved. From the viewpoint of reducing the dielectric loss tangent, the roughness Rz of the copper foil surface is more preferably 0.5 μm or more, still more preferably 0.6 μm or more, particularly preferably 0.7 μm or more, and more preferably is 3.5 μm or less, more preferably 3.0 μm or less, particularly preferably 2.0 μm or less.

Examples of the lamination molding method include methods normally used when molding laminate boards for printed wiring boards and multilayer boards, and more specifically, multistage press machines, multistage vacuum press machines, continuous molding machines, autoclave molding machines, etc. An example of this is a method of laminated molding at a temperature of about 180 to 350° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg/cm ² . Furthermore, a multilayer board can be obtained by laminating and molding a combination of the prepreg of this embodiment and a separately produced wiring board for an inner layer. As a method for manufacturing a multilayer board, for example, copper foil of about 35 μm is placed on both sides of one sheet of prepreg of this embodiment, and after lamination is formed using the above-mentioned forming method, an inner layer circuit is formed, and this circuit is coated with black. After that, the inner layer circuit board and the prepreg of this embodiment are alternately placed one by one, and a copper foil is placed on the outermost layer, and the above conditions are met. A multilayer board can be produced by lamination molding, preferably under vacuum. The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.

As described above, the resin composition for electronic materials obtained using the resin composition of the present embodiment (resin composition consisting of a combination of specific components) has low dielectric properties (low dielectric constant and/or In addition to being excellent in low dielectric loss tangent (or low dielectric loss tangent) and low thermal expansion, it can also have excellent properties in heat resistance (glass transition temperature) and desmear resistance.

<<Printed wiring board>>
The printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, the insulating layer being formed from the resin composition of the present embodiment. and a layer formed from the prepreg of this embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited.

More specifically, first, a metal foil-clad laminate (such as a copper foil-clad laminate) is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. The surface of the inner layer circuit of this inner layer substrate is subjected to surface treatment to increase adhesive strength as required, and then the cured product of the resin composition of this embodiment or prepreg is layered on the surface of the inner layer circuit, and then the outside A metal foil for the outer layer circuit is laminated on the top and the metal foil is heated and pressed to form an integral mold. In this way, a laminate is produced that has an insulating layer formed from a cured resin composition or a prepreg between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this laminate, a desmear process is performed to remove smear, which is resin residue derived from the resin component contained in the cured material layer. After that, a plating metal film is formed on the wall of the hole for the through hole or via hole to provide electrical continuity between the inner layer circuit and the metal foil for the outer layer circuit, and if necessary, the metal foil for the outer layer circuit is etched. Form the outer layer circuit. Alternatively, in the case of the subtractive method, a circuit pattern is formed using a photoresist after electroless copper plating and electrolytic copper plating on the via wall surface. After that, in order to protect the circuit pattern other than the parts to be soldered to each member, solder resist is applied to both sides and openings are made in the parts where solder connections are required. At that time, since openings are formed at different locations on the front and back sides of the laminate, the problem of back exposure occurs. The cured product of the resin composition of this embodiment has low transmittance for G-line (wavelength 436 nm), H-line (wavelength 405 nm), and I-line (wavelength 365 nm) even when the cured product has a thickness of 30 μm. This back exposure problem can be effectively suppressed.
After exposure, a printed wiring board is manufactured by performing appropriate processing.

In addition, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer that will become a circuit on the cured product of the resin composition of this embodiment or a prepreg. At this time, an electroless plating method can also be used to form the conductor layer.

More specifically, the printed wiring board of this embodiment includes, for example, at least one insulating layer containing a cured product of the resin composition of this embodiment, and at least one conductor layer in contact with the insulating layer. a step of forming a photosensitive composition layer that is cured by light with a wavelength of 350 to 440 nm on both sides of the substrate, and disposing a mask pattern on at least one side of the photosensitive composition layer, and passing through the mask pattern. The printed wiring board can be manufactured by a method for manufacturing a printed wiring board, which includes a step of exposing to light with a wavelength of 350 to 440 nm.
Furthermore, the printed wiring board of the present embodiment includes a substrate in which at least one insulating layer containing the cured product of the resin composition of the present embodiment and at least one conductive layer in contact with the insulating layer are laminated. a step of forming a photosensitive composition layer that is cured by light with a wavelength of 350 to 440 nm on both sides of the substrate, and arranging a mask pattern on at least one side of the photosensitive composition layer, It can be manufactured by a method for manufacturing a printed wiring board, which includes the step of exposing light with a wavelength of 350 to 440 nm through the mask pattern.
In addition, as a photosensitive composition layer, a solder resist layer is mentioned, for example. As the solder resist, commercially available ones can be used. Known methods can be used for exposure, such as contact exposure in which the mask pattern is exposed to the photosensitive composition layer in close contact with the photosensitive composition layer, or projection exposure in which the mask pattern and the photosensitive composition layer are exposed without being in close contact with each other. Good too.
By using the resin composition of this embodiment for the insulating layer of a printed wiring board, back exposure can be suppressed. The thickness of the insulating layer containing the cured product of the resin composition of the present embodiment can be appropriately selected depending on the intensity of light used for exposure, and is not particularly limited. Hereinafter, the thickness is 30 μm or less and 15 μm or less. The lower limit of the thickness of the insulating layer is, for example, 0.1 μm or more, but may be 5 μm or more, or 10 μm or more. Examples of the insulating layer containing the cured product of the resin composition of this embodiment include a layer formed from the resin composition of this embodiment and a layer formed from the prepreg of this embodiment.
Further, in the method for manufacturing a printed wiring board of the present embodiment, the number of insulating layers containing the cured product of the resin composition of the present embodiment in the printed wiring board may be at least one, and may be two or more. Good too. Further, it may be used in combination with an insulating layer containing a cured product other than the resin composition of this embodiment.

Further, in the method for manufacturing a coreless printed wiring board, for example, instead of the step of preparing the printed wiring board as described above, a step of preparing a core substrate, and a step of including the composition of the present embodiment on the core substrate. A step is performed to obtain a laminate in which at least one insulating layer and a conductor layer disposed on the outermost surface of the insulating layer are stacked. That is, by laminating one or more insulating layers and one or more conductor layers on a core substrate, a laminate in which a buildup layer is formed on the core substrate can be obtained. Thereafter, the core substrate is removed (separated) to form a coreless printed wiring board (also referred to as a coreless substrate).

Then, by performing the steps of forming a photosensitive composition layer and exposing the coreless substrate to light in the same manner as described above, a coreless printed wiring board on which a circuit pattern is formed can be obtained.

The present embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, the descriptions in paragraphs 0200 to 0202 of JP-A-2021-021027 can be referred to, and the contents thereof are incorporated into this specification.

Furthermore, it is preferable that the insulating layer formed of the cured product of the resin composition of the present embodiment has a reduced surface roughness after the insulating layer is subjected to a roughening treatment. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness Ra is not particularly limited, but may be, for example, 10 nm or more. The arithmetic mean roughness Ra of the surface of the insulating layer was measured using a shape measuring microscope (laser microscope, VK-X210 (trade name) manufactured by Keyence Corporation) with an objective lens magnification of 150 times, and the image was The height distribution on a straight line with a length of 90 μm randomly selected was determined by image processing.

<<Resin composite sheet>>
The resin composite sheet of this embodiment includes a support and a layer formed from the resin composition of this embodiment disposed on the surface of the support. The resin composite sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin composite sheet is not particularly limited, but for example, the resin composite sheet may be produced by applying (coating) a solution in which the resin composition of the present embodiment described above is dissolved in a solvent to a support and drying it. There are several ways to obtain it.

Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and release films in which a release agent is applied to the surface of these films. Examples include organic film base materials such as polyimide film, conductive foils such as copper foil and aluminum foil, plate-like materials such as glass plates, SUS (Steel Use Stainless) plates, and FRP (Fiber-Reinforced Plastics). It is not particularly limited.

Examples of the coating method (coating method) include a method in which a solution of the resin composition of the present embodiment dissolved in a solvent is coated onto the support using a bar coater, die coater, doctor blade, Baker applicator, etc. It will be done. Further, after drying, the support can be peeled off or etched from the resin composite sheet in which the support and the resin composition are laminated, thereby forming a single layer sheet. Note that the support can be used by supplying a solution in which the resin composition of the present embodiment described above is dissolved in a solvent into a mold having a sheet-like cavity and drying it to form it into a sheet. It is also possible to obtain a single layer sheet.

In the production of the single-layer sheet or resin composite sheet of this embodiment, the drying conditions for removing the solvent are not particularly limited, but if the temperature is low, the solvent tends to remain in the resin composition, and if the temperature is high, Since curing of the resin composition progresses, the temperature is preferably 20° C. to 200° C. for 1 to 90 minutes. Further, the single layer sheet or the resin composite sheet can be used in an uncured state where the solvent is simply dried, or it can be used in a semi-cured (B-staged) state if necessary. Further, the thickness of the resin layer in the single-layer sheet or resin composite sheet of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment used for application (coating) and the coating thickness, and there are no particular limitations. However, in general, as the coating thickness increases, solvent tends to remain during drying, so it is preferably 0.1 μm or more, and the upper limit may be 500 μm or less, 200 μm or less, or 180 μm or less. However, it is also possible to form a thin film with a thickness of 100 μm or less, 80 μm or less, 30 μm or less, or 15 μm or less.

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
If the measuring equipment used in the examples is difficult to obtain due to discontinuation or the like, measurement can be performed using other equipment with equivalent performance.

<Measurement of weight average molecular weight and number average molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin and compound were measured by gel permeation chromatography (GPC). Liquid pump (manufactured by Shimadzu Corporation, LC-20AD), differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A), GPC column (manufactured by Showa Denko Corporation, GPC KF-801, 802, 803, 804) The experiment was carried out using tetrahydrofuran as the solvent, a flow rate of 1.0 mL/min, a column temperature of 40° C., and a calibration curve using monodisperse polystyrene.

<Synthesis Example 1 Synthesis of naphthol aralkyl cyanate ester compound (SNCN)>
1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane, This was designated as solution 1.
Cyanogen chloride 125.9 g (2.05 mol) (1.6 mol per 1 mol of hydroxy group), dichloromethane 293.8 g, 36% hydrochloric acid 194.5 g (1.92 mol) (1.5 mol per 1 mol of hydroxy group) ), Solution 1 was poured into 1205.9 g of water over 30 minutes while stirring and keeping the liquid temperature between -2°C and -0.5°C. After pouring Solution 1, after stirring at the same temperature for 30 minutes, a solution (Solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol per 1 mol of hydroxyl group) was dissolved in 65 g of dichloromethane was added to 10 g of dichloromethane. I poured it over several minutes. After pouring the second solution, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.
Thereafter, the reaction solution was allowed to stand still to separate the organic phase and the aqueous phase. The resulting organic phase was washed five times with 1300 g of water. The electrical conductivity of the waste water after the fifth washing with water was 5 μS/cm, confirming that the ionic compounds to be removed were sufficiently removed by washing with water.
The organic phase after washing with water was concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl cyanate ester compound (SNCN) (orange viscous material). The weight average molecular weight of the obtained SNCN was 600. Further, the IR spectrum of SNCN showed absorption at 2250 cm ^-1 (cyanate ester group) and no absorption at hydroxyl group.

<Synthesis Example 2 Synthesis of modified polyphenylene ether compound>
<<Synthesis of bifunctional phenylene ether oligomer>>
9.36 g (42.1 mmol) of CuBr ₂ and 1.81 g (10 mmol) of N,N'-di-t-butylethylenediamine were placed in a 12 L vertical reactor equipped with a stirrer, thermometer, air inlet tube, and baffle plate. .5 mmol), n-butyldimethylamine 67.77 g (671.0 mmol), and toluene 2,600 g were stirred at a reaction temperature of 40°C. 3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol 129.32 g (0.48 mol), 2,6-dimethylphenol 878.4 g (7.2 mol) A mixed solution of 1.22 g (7.2 mmol) of N,N'-di-t-butylethylenediamine and 26.35 g (260.9 mmol) of n-butyldimethylamine was mixed with nitrogen and air to give an oxygen concentration of 8. A mixed gas adjusted to volume % was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 L/min, followed by stirring. After the dropwise addition was completed, 1,500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated to 50% by mass using an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). Resin "A" had a number average molecular weight in terms of polystyrene determined by GPC of 1,975, a weight average molecular weight in terms of polystyrene determined by GPC of 3,514, and a hydroxyl equivalent of 990.

<<Synthesis of modified polyphenylene ether compound>>
In a reactor equipped with a stirring device, a thermometer, and a reflux tube, 833.4 g of a toluene solution of resin "A", 76.7 g of vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-P"), 1 methylene chloride, 600 g of benzyldimethylamine, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 40°C. After stirring for 24 hours, the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated using an evaporator, solidified by dropping into methanol, and the solid was collected by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The modified polyphenylene ether compound had a number average molecular weight in terms of polystyrene determined by GPC of 2,250, a weight average molecular weight in terms of polystyrene determined by GPC of 3,920, and a vinyl group equivalent of 1189 g/vinyl group.

Example 1
15.0 parts by mass of the naphthol aralkyl cyanate ester compound synthesized in Synthesis Example 1, 35.0 parts by mass of bismaleimide (BMI-80, manufactured by K.I. Kasei Co., Ltd.) having the structure shown below, obtained in Synthesis Example 2. 25.0 parts by mass of modified polyphenylene ether compound, 15.0 parts by mass of phosphorus flame retardant (PX-200, manufactured by Daihachi Kagaku Co., Ltd., 1,3-phenylene bis(2,6-dixylenyl phosphate)), styrene Oligomer (Crystalex 3085, manufactured by Eastman Chemical Co.) 5.0 parts by mass, thermoplastic elastomer (SEPS, manufactured by Kuraray Co., Ltd., SEPTON 2104) 5.0 parts by mass, silica (average particle size 1.1 μm, manufactured by Admatex Co., Ltd.) SC4500SQ classified product) 62.5 parts by mass, silica (average particle size 0.7 μm, SFP-130MC, manufactured by Denki Kagaku Kogyo Co., Ltd.) 62.5 parts by mass, wetting and dispersing agent (DISPERBYK-161, manufactured by BYK Company) 1. 0 parts by mass, silane coupling agent (KBM403, manufactured by Shin-Etsu Silicone) 3.0 parts by mass, wetting and dispersing agent (DISPERBYK-2009, manufactured by BYK) 0.4 parts by mass, ultraviolet absorber (HR-1, Central Synthesis) 0.5 parts by mass of non-metallic organic dye (Kayaset Black AN, manufactured by Nippon Kayaku Co., Ltd.), 0.005 parts by mass of manganese octylate, and 0.9 parts by mass of triphenylimidazole. A mass part was dissolved in methyl ethyl ketone and mixed to obtain a varnish. Note that each amount added above indicates the amount of solid content.
BMI-80
Me represents a methyl group.

<Manufacture of a test piece of a cured plate with a thickness of 0.8 mm>
A resin composition powder was obtained by evaporating the solvent from the obtained varnish. A mold with a side of 100 mm and a thickness of 0.8 mm was filled with the resin composition powder, copper foil (3EC-M2S-VLP, manufactured by Mitsui Mining & Mining Co., Ltd.) with a thickness of 12 μm was placed on both sides, and a pressure of 30 kg/ cm ² and a temperature of 220° C. for 120 minutes, and then the copper foil on both sides was removed by etching to obtain a cured plate with a side of 100 mm and a thickness of 0.8 mm.
Using the obtained cured plate, the dielectric constant (Dk), dielectric loss tangent (Df), and glass transition temperature (Tanδ) were evaluated. The evaluation results are shown in Table 1.

<Manufacture of a 30 μm thick hardened plate test piece>
The obtained varnish was applied to a copper foil base material (1.5 μm thick copper foil (MT-FL, manufactured by Mitsui Kinzoku Mining Co., Ltd.)) so that the thickness of the resin composition layer after drying was 30 μm. The solvent was removed by drying at 150°C for 3 minutes, and a 12 μm thick copper foil (3EC-M2S-VLP, manufactured by Mitsui Kinzoku Mining Co., Ltd.) was placed on the other side at a pressure of 30 kg/cm ² and a temperature of 220°C. Vacuum pressing was performed for 120 minutes to obtain a copper foil-clad laminate having a side of 200 mm and a thickness of 30 μm. The copper foil of the obtained copper foil-clad laminate was removed by etching to obtain a sample for evaluation (cured plate with a thickness of 30 μm). Using the produced evaluation sample, the light transmittance of g-line, h-line, and i-line, and back exposure were evaluated. The evaluation results are shown in Table 1.

<Measurement method and evaluation method>
(1) Measurement of light transmittance of g-line (436 nm), h-line (405 nm), and i-line (365 nm) The prepared evaluation sample with a thickness of 30 μm was measured using a UV-vis measuring device (manufactured by Hitachi High-Technologies Corporation). The light transmittance at wavelengths of 365 nm, 405 nm, and 436 nm was measured using a Hitachi spectrophotometer (U-4100).
The unit is shown in %.

(2) Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df) The cured plate with a thickness of 0.8 mm obtained above was processed into a size of 1.0 mm x 100 mm and dried at 120° C. for 60 minutes. Thereafter, the relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying at 10 GHz were measured using a perturbation method cavity resonator. The measurement temperature was 23°C.
The perturbation method cavity resonator used was Agilent 8722ES manufactured by Agilent Technologies.
Specific permittivity (Dk)
A: 3.0 or less B: 3.0 super dielectric loss tangent (Df)
S: Less than 0.0026 A: 0.0026 or more and less than 0.0027 B: 0.0027 or more and less than 0.0028 C: 0.0028 or more

(3) Judgment of back exposure A 15 μm thick film resist (PSR-800 AUS SR1 manufactured by Taiyo Holdings Co., Ltd.) was laminated on both sides of the prepared evaluation sample with a thickness of 30 μm, and one side ( The exposed surface was exposed under the following conditions. Thereafter, the uncured resist on the surface opposite to the exposed surface (back surface) was removed. On the back side, it was confirmed whether or not any resist residue remained by back exposure from the exposed side.
Equipment: ORC DI exposure machine Light source: 3 types of mixture (g-line, h-line, i-line)
Exposure amount: 400mJ
A: No resist residue B: With resist residue

(4) Glass transition temperature (Tanδ)
The cured plate with a thickness of 0.8 mm obtained above was processed into a size of 12.7 mm x 30 mm, and measured using a dynamic viscoelasticity measuring device according to JIS-K7244-4:1999 (Plastics - dynamic mechanical properties). Test method - Part 4: Tensile vibration - non-resonance method), the dynamic viscoelasticity was measured at a starting temperature of 30°C, an ending temperature of 400°C, a heating rate of 5°C/min, a measurement frequency of 1Hz, and a nitrogen atmosphere. It was measured. The temperature at which the loss tangent (Tan δ) obtained at that time had a maximum value was defined as the glass transition temperature.
The dynamic viscoelasticity measuring device used was EXSTAR6000 DMS6100 manufactured by Seiko Instruments Inc.
It was evaluated as follows.
A: 255°C or more B: 245°C or more and less than 255°C C: Less than 245°C

Example 2
Example 1 was carried out in the same manner as in Example 1 except that the content of the non-metallic organic dye (Kayaset Black AN) was changed to 1.0 parts by mass.

Example 3
In Example 1, the content of the ultraviolet absorber (HR-1) was changed to 1.0 parts by mass, and the content of the nonmetallic organic dye (Kayaset Black AN) was changed to 1.0 parts by mass. The others did the same thing.

Example 4
The same procedure as in Example 1 was carried out except that the ultraviolet absorber (HR-1) was not blended and the content of the non-metallic organic dye (Kayaset Black AN) was changed to 2.0 parts by mass.

Example 5
Example 1 was carried out in the same manner as in Example 1 except that the content of the non-metallic organic dye (Kayaset Black AN) was changed to 2.0 parts by mass.

Example 6
In Example 1, the content of the ultraviolet absorber (HR-1) was changed to 3.0 parts by mass, and the content of the nonmetallic organic dye (Kayaset Black AN) was changed to 1.0 parts by mass. The others did the same thing.

Comparative example 1
Example 1 was carried out in the same manner as in Example 1, except that the ultraviolet absorber (HR-1) and the non-metallic organic dye (Kayaset Black AN) were not blended.

Comparative example 2
Example 1 was carried out in the same manner as in Example 1, except that the non-metallic organic dye (Kayaset Black AN) was not blended.

Comparative example 3
In Example 1, the content of the ultraviolet absorber (HR-1) was changed to 3.0 parts by mass, and the nonmetallic organic dye (Kayaset Black AN) was not blended, but the other steps were the same. .

Comparative example 4
The same procedure as in Example 1 was carried out except that the ultraviolet absorber (HR-1) was not blended and the content of the non-metallic organic dye (Kayaset Black AN) was changed to 1.0 parts by mass.

Claims

A resin composition containing a thermosetting compound,
A resin composition in which the transmittance of g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm) in a cured product molded to a thickness of 30 μm is 0.070% or less, respectively. thing.
The resin composition according to claim 1, wherein the cured product molded to a thickness of 30 μm has a transmittance of H-line (wavelength 405 nm) of 0.050% or less.
The resin composition according to claim 1 or 2, wherein the cured product molded to a thickness of 30 μm has an i-line (wavelength 365 nm) transmittance of 0.040% or less.
The resin composition according to claim 1 or 2, comprising an ultraviolet absorber and/or a non-metallic organic dye.
The resin composition according to claim 1 or 2, comprising an ultraviolet absorber and a non-metallic organic dye.
The resin composition according to claim 4, wherein the nonmetallic organic pigment contains a dye.
The resin composition according to claim 4, wherein the content of the ultraviolet absorber is more than 0 parts by mass and 3.0 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition.
The resin composition according to claim 4, wherein the content of the nonmetallic organic dye is more than 0 parts by mass and 2.0 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition.
The resin composition according to claim 5, wherein the mass ratio of the ultraviolet absorber and the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is 0.15 to 4.0.
The resin composition according to claim 5, wherein the mass ratio of the ultraviolet absorber to the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is 0.4 to 1.5.
The thermosetting compound includes a maleimide compound, an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and a structural unit represented by formula (V). The resin composition according to claim 1 or 2, comprising one or more selected from the group consisting of a cyanate ester compound and a cyanate ester compound.
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
The resin composition according to claim 1 or 2, wherein a dielectric loss tangent of a cured product of the resin composition is 0.0001 or more and less than 0.0027.
The resin composition according to claim 1 or 2, further comprising a filler.
The resin composition according to claim 13, wherein the content of the filler is 10 to 1000 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
The resin composition according to claim 1 or 2, which is used for forming an insulating layer.
The transmittance of the H-line (wavelength 405 nm) in the cured product molded to a thickness of 30 μm is 0.050% or less,
The transmittance of i-line (wavelength 365 nm) in the cured product molded to a thickness of 30 μm is 0.040% or less,
Contains UV absorbers and non-metallic organic pigments,
the non-metallic organic pigment contains a dye,
The content of the ultraviolet absorber is more than 0 parts by mass and 3.0 parts by mass or less with respect to 100 parts by mass of resin solid content in the resin composition,
The content of the non-metallic organic dye is more than 0 parts by mass and 2.0 parts by mass or less with respect to 100 parts by mass of resin solid content in the resin composition,
The mass ratio of the ultraviolet absorber and the nonmetallic organic dye (ultraviolet absorber/nonmetallic organic dye) is 0.4 to 1.5,
The thermosetting compound includes a maleimide compound, an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and a structural unit represented by formula (V). 2. The resin composition according to claim 1, comprising one or more selected from the group consisting of a cyanate ester compound and a cyanate ester compound.
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
A cured product of the resin composition according to claim 1, 2 or 16.
A prepreg formed from a base material and the resin composition according to claim 1, 2, or 16.
A metal foil-clad laminate comprising a layer formed from the resin composition according to claim 1, 2 or 16, and metal foil disposed on one or both sides of the layer.
A resin composite sheet comprising a support and a layer formed from the resin composition according to claim 1, 2 or 16 disposed on the surface of the support.
A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, the insulating layer comprising a layer formed from the resin composition according to claim 1, 2 or 16. , printed wiring board.
The printed wiring board according to claim 21, wherein the insulating layer has an insulating layer having a thickness of 15 μm or less.
A semiconductor device comprising the printed wiring board according to claim 22.
at least one insulating layer comprising a cured product of the resin composition according to claim 1, 2 or 16;
a step of preparing a substrate laminated with at least one conductor layer in contact with the insulating layer;
forming a photosensitive composition layer that is cured by light with a wavelength of 350 to 440 nm on both sides of the substrate;
arranging a mask pattern on at least one surface of the photosensitive composition layer, and exposing the photosensitive composition layer to light with a wavelength of 350 to 440 nm through the mask pattern,
A method for manufacturing printed wiring boards.
A substrate having at least one insulating layer containing a cured product of the resin composition according to claim 1, 2, or 16 and at least one conductive layer in contact with the insulating layer is coated with a substrate having a wavelength of 350 to 350, respectively. forming a photosensitive composition layer that is cured by 440 nm light;
arranging a mask pattern on at least one surface of the photosensitive composition layer, and exposing the photosensitive composition layer to light with a wavelength of 350 to 440 nm through the mask pattern,
A method for manufacturing printed wiring boards.
The method for manufacturing a printed wiring board according to claim 24, wherein the insulating layer has an insulating layer having a thickness of 15 μm or less.