JP2023180708A - Curable resin composition and cured product - Google Patents

Abstract

To provide a novel radical polymerization initiator for a curable resin composition while preventing the deterioration of the dielectric loss tangent of a cured product.SOLUTION: A curable resin composition includes a compound A that includes a dioxane skeleton and a methacryloyl group in at least one end of the molecular chain, and a radical curable resin. The content of the compound A is 0.01-20 mass% relative to the total amount of the curable resin composition. The content of the radical curable resin is 10-99.99 mass% relative to the total amount of the curable resin composition.SELECTED DRAWING: None

Description

The present invention relates to the use of a compound having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain as a curable resin composition, a cured product, and a radical polymerization initiator.

In recent years, as the fields of use for substrates on which electrical and electronic components are mounted have expanded, the required characteristics have become broader and more sophisticated. Among these, in particular, the fifth generation communication system "5G", for which research and development is accelerating, is expected to further increase capacity and speed, and the need for low dielectric loss tangent materials for use in it is expected to increase. It's coming. Therefore, various studies have been made to produce resins with low dielectric loss tangents.

For example, Patent Document 1 describes the provision of a curable resin composition having a specific structure with excellent high heat resistance and low dielectric properties, which is suitably used for sealing electrical and electronic components, circuit boards, etc. For this purpose, maleimide resins having a certain structure are disclosed. Furthermore, it is disclosed that it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of a radically polymerizable curable resin such as maleimide resin or radical polymerization with other components.

Japanese Patent Application Publication No. 2020-176190

However, as a result of intensive studies by the present inventors, it has been found that depending on the type of compound such as a radical polymerization initiator used in the curable resin composition, a problem may occur in which the dielectric loss tangent of the resulting cured product deteriorates. I've come to understand.

Therefore, the present invention has been made in view of the above-mentioned problems, and aims to provide a novel radical polymerization initiator for curable resin compositions while preventing the deterioration of the dielectric loss tangent of the cured product. .

As a result of intensive studies to solve the above problems, the present inventors surprisingly discovered a compound with a specific structure having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain. was found to be a radical polymerizable monomer as well as a radical polymerization initiator, leading to the completion of the present invention.

The present invention includes the following embodiments.
[1]
A compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain;
A radical curable resin;
The content of the compound A is 0.01 to 20% by mass based on the total amount of the curable resin composition,
The content of the radical curable resin is 10 to 99.99% by mass based on the total amount of the curable resin composition.
Curable resin composition.
[2]
The compound A has a spiro ring skeleton,
At least one ring structure constituting the spiro ring skeleton has the dioxane skeleton,
The curable resin composition according to [1].
[3]
The spiro ring skeleton has a spiro-fused skeleton of two dioxane skeletons,
The curable resin composition according to [1] or [2].
[4]
the compound A is spiroglycol acrylate or spiroglycol diacrylate;
The curable resin composition according to any one of [1] to [3].
[5]
The compound A has a dispiro ring skeleton,
At least one ring structure constituting the dispiro ring skeleton has the dioxane skeleton,
The curable resin composition according to any one of [1] to [4].
[6]
The dispiro ring skeleton has a skeleton in which two dioxane skeletons are each spiro-fused to a cyclohexane skeleton,
The curable resin composition according to any one of [1] to [5].
[7]
The radical curable resin contains one or more functional groups selected from the group consisting of an ethylenically unsaturated bond, a (meth)acryloyl group, a maleimide group, and a vinyl group.
The curable resin composition according to any one of [1] to [6].
[8]
A cured product obtained by curing the curable resin composition according to any one of [1] to [7],
The dielectric loss tangent (10GHz) is 0.006 or less,
cured product.
[9]
The curing temperature is 200°C or less,
The curable resin composition according to any one of [1] to [7].
[10]
As a radical polymerization initiator,
Use of compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain.

According to the present invention, it is possible to provide a novel radical polymerization initiator for a curable resin composition while preventing deterioration of the dielectric loss tangent of a cured product.

Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. It is.

1. Curable Resin Composition The curable resin composition of the present embodiment includes a compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain, and a radical curable resin, The content of the compound A is 0.01 to 20% by mass based on the total amount of the curable resin composition, and the content of the radical curable resin is 10 to 20% by mass based on the total amount of the curable resin composition. It is 99.99% by mass. Each component will be explained in detail below.

1.1. Compound A
Compound A of this embodiment is a compound having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain. Compound A, as a radical polymerization initiator, generates radicals by heating and can cure the radical-curable resin described below.

Conventionally, Compound A has been used as a polymerizable monomer in curable resin compositions, but its use as a radical polymerization initiator has not been studied. Therefore, the present inventors conducted extensive studies and found that when compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain is used as a radical polymerization initiator for a radical curable resin. It has been found that the cured product has properties that make it difficult to deteriorate the dielectric properties such as the dielectric loss tangent. Further, since Compound A has a relatively low curing temperature compared to other radical polymerization initiators, it is preferable from the viewpoints of energy efficiency, equipment construction, cost, and the like. Hereinafter, the structure of Compound A and the use of Compound A as a radical polymerization initiator will be explained in detail.

Compound A is a compound having a (meth)acryloyl group at at least one end of its molecular chain. Further, from the viewpoint of reducing the content of the radical polymerization initiator in the curable resin composition, it is preferable to have (meth)acryloyl groups at both ends of the molecular chain.

Examples of the dioxane skeleton include a 1,3-dioxane skeleton and a 1,4-dioxane skeleton, and from the viewpoint of lowering the dielectric loss tangent of the cured product, it is preferable to have a 1,3-dioxane skeleton.

The specific structure of compound A is not particularly limited, and examples thereof include compounds represented by the following formulas (1) to (3). The compounds represented by the following formulas (1) to (3) will be explained in detail below.

Compound A may be a compound represented by the following formula (1) from the viewpoint of lowering the dielectric loss tangent of the cured product and lowering the curing temperature.


(In formula (1), R ¹¹ and R ¹³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms.In addition, R ¹² and R ¹⁴ each independently represent a single bond or an aliphatic group having 1 to 12 carbon atoms. Represents an organic group selected from the group consisting of a group hydrocarbon group, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms.In addition, an aliphatic hydrocarbon group may be either linear or branched.)

In the above formula (1), R ¹¹ and R ¹³ are preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 9 carbon atoms. group, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Further, R ¹² and R ¹⁴ are preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 9 carbon atoms, and even more preferably 1 to 6 carbon atoms. is an aliphatic hydrocarbon group.

More specific structures of the above formula (1) are not particularly limited, but include, for example, compounds represented by the following formulas (1-1) to (1-12).

Further, the compound A of the present embodiment may have a spiro ring skeleton, and at least one ring structure constituting the spiro ring skeleton may have a structure having the dioxane skeleton. In addition, from the viewpoint of lowering the dielectric loss tangent of the cured product and lowering the curing temperature, as represented by the following formula (2), the spiro ring skeleton has a skeleton in which two dioxane skeletons are spiro-condensed. It is preferable. Moreover, from the viewpoint of manufacturing cost, etc., it is also preferable to use spiroglycol acrylate or spiroglycol diacrylate.

(In formula (2), R ²¹ and R ²³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ²² and R ²⁴ each independently represent a single bond or an aliphatic group having 1 to 12 carbon atoms. Represents an organic group selected from the group consisting of a group hydrocarbon group, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms.In addition, an aliphatic hydrocarbon group may be either linear or branched.)

In the above formula (2), R ²¹ and R ²³ are preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 9 carbon atoms. group, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Further, R ²² and R ²⁴ are preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 9 carbon atoms, and still more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms. is an aliphatic hydrocarbon group.

More specific structures of the above formula (2) are not particularly limited, but include, for example, compounds represented by the following formulas (2-1) to (2-12).

Furthermore, the compound A of the present embodiment has a dispiro ring skeleton, and at least one ring structure constituting the dispiro ring skeleton may have a dioxane skeleton. In addition, from the viewpoint of lowering the dielectric loss tangent of the cured product and lowering the curing temperature, it is possible to use a skeleton in which two dioxane skeletons are spirocondensed to a cyclohexane skeleton, as shown in the following formula (3). It is preferable to have.

(In formula (3), R ³¹ and R ³³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ³² and R ³⁴ each independently represent a single bond or an aliphatic group having 1 to 12 carbon atoms. Represents an organic group selected from the group consisting of a group hydrocarbon group, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms.In addition, an aliphatic hydrocarbon group may be either linear or branched.)

In the above formula (3), R ³¹ and R ³³ are preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 9 carbon atoms. group, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Further, R ³² and R ³⁴ are preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 9 carbon atoms, and even more preferably 1 to 6 carbon atoms. is an aliphatic hydrocarbon group.

More specific structures of the above formula (3) are not particularly limited, but include, for example, compounds represented by the following formulas (3-1) to (3-12).

The content of compound A in this embodiment is 0.01 to 20% by mass, preferably 0.05 to 15% by mass, more preferably 0.10 to 15% by mass, based on the total amount of the curable resin composition. The content is 10% by mass, more preferably 0.50 to 5.0% by mass, even more preferably 1.0 to 5.0% by mass.

1.2. Method for producing compound A As a method for producing compound A, conventionally known methods can be used. A specific example will be explained in detail below.

The method for synthesizing the compound of chemical formula (1) is not particularly limited, but for example, a terminal functional group of a compound produced by dehydration condensation of a predetermined carbonyl compound and a predetermined polyol under an acid catalyst is acryloylated. This can be obtained by

In addition, the method for synthesizing the compound of chemical formula (2) is not particularly limited, but for example, a terminal functionalization of a compound produced by dehydration condensation of a predetermined carbonyl compound and a predetermined pentaerythritol derivative under an acid catalyst. It can be obtained by acryloylating a group or the like. Regarding spiroglycol acrylate and spiroglycol diacrylate, commercially available spiroglycol (3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro [5. It may be synthesized by acryloylating the terminal using 5] undecane).

The method for synthesizing the compound of chemical formula (3) is not particularly limited, but for example, the terminal functional group of a compound produced by dehydration condensation of a predetermined 1,4-cyclohexanedione derivative and a predetermined polyol under an acid catalyst. It may also be synthesized by acryloylating.

1.3. Radical curable resin The radical curable resin is not particularly limited as long as it can perform intermolecular crosslinking by radical reaction, but examples include unsaturated polyester resins and radically polymerizable group-introduced polymers. . Each will be explained in detail below.

The radical curable resin of this embodiment is selected from the group consisting of ethylenically unsaturated bonds, (meth)acryloyl groups, maleimide groups, and vinyl groups from the viewpoint of combination with compound A used as a radical polymerization initiator. It is preferable to include one or more functional groups.

Further, the radical curable resin in this embodiment may include a compound that is polymerized by a radical reaction and becomes a cured product. Such a compound may be a single compound or may be composed of two or more compounds. Further, the radical curable resin may have a resin or compound that is not a radical curable resin in its structure as a copolymerization component.

The unsaturated polyester resin is not particularly limited as long as it has ethylenically unsaturated bonds in its structure, but for example, it can be made by mixing a dibasic acid containing an unsaturated dibasic acid and a polyol in a desired ratio. It may be synthesized by subsequent dehydration condensation and esterification. Alternatively, by first reacting a polyol with a saturated dibasic acid, carbonic ester, etc., a polymer diol having alcohol groups at both ends is formed, and the resulting polymer diol is reacted with an unsaturated dibasic acid. An unsaturated polyester resin may be synthesized by Note that the ethylenically unsaturated bond means a carbon-carbon double bond that can undergo radical polymerization.

Moreover, as such a polymer diol, polycarbonate diol is preferable from the viewpoint of lowering the dielectric loss tangent. In that case, first, by reacting a predetermined polyol with a predetermined carbonate ester, etc. in a predetermined stoichiometric ratio, a polycarbonate diol having alcohol groups at both ends is formed, and then an unsaturated dibase is added to the polycarbonate diol. By reacting with an acid, an unsaturated polyester resin having a polycarbonate skeleton can be obtained.

The polyol component constituting the unsaturated polyester resin is not particularly limited, but includes, for example, aliphatic diols, alicyclic diols, alkylene oxide adducts of bisphenol, alkylene oxide adducts of aromatic dihydroxy compounds, aromatic diols, etc. Can be mentioned. More specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,3-pentanediol , 2,4-pentanediol, 2-methyl-1,3-butanediol, neopentyl glycol, 1,3-hexanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 2- Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol, 2-ethyl-1,5-pentanediol, 2-propyl-1,5-pentanediol, 2 ,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,2- Propanediol, 1,4-butanediol, 1,6-hexanediol, 2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol, polyethylene glycol , polypropylene glycol and polybutylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-bis (hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexane, 1,2-decahydronaphthalene dimethanol, 1,3-decahydronaphthalene dimethanol, 1,4-decahydronaphthalene dimethanol, 1,5 -Decahydronaphthalene dimethanol, 1,6-decahydronaphthalene dimethanol, 2,7-decahydronaphthalene dimethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, 5-methylol-5-ethyl-2 -(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, pentacyclododecane dimethanol and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8, 10-tetraoxaspiro[5.5]undecane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane (bisphenol F), 1,1-bis(4- hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis( 4-hydroxyphenyl)pentane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 4,4'-dihydroxydiphenyl ether, 4 , 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxydiphenyl sulfone, hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether and 4,4' -dihydroxydiphenylbenzophenone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane (bisphenol F), 1,1-bis(4-hydroxyphenyl)ethane, 1, 1-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide , 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenylbenzophenone. It will be done. Furthermore, trifunctional or higher functional polyols are not particularly limited, but include, for example, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

The unsaturated dibasic acid component constituting the unsaturated polyester resin is not particularly limited, and examples thereof include maleic acid, fumaric acid, itaconic acid, and citraconic acid.

When the unsaturated polyester resin has a polycarbonate skeleton, the carbonate component constituting the skeleton is not particularly limited, but includes, for example, diphenyl carbonate, ditolyl carbonate, bischlorophenyl carbonate, m-cresyl carbonate, dimethyl carbonate, Examples include diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like.

Conventionally known methods can be used to produce the unsaturated polyester resin, and examples include, but are not limited to, melt polymerization methods such as transesterification and direct esterification, or solution polymerization. . Furthermore, conventionally known transesterification catalysts and the like can be used.

Transesterification catalysts are not particularly limited, but include, for example, catalysts containing manganese and catalysts containing titanium. Examples of catalysts containing manganese include fatty acid manganese salts such as manganese acetate, manganese carbonate, manganese chloride, and manganese. Examples include acetylacetonate salt, manganese hydroxide, and the like.

Catalysts containing titanium are not particularly limited, but include, for example, tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, Titanium alkoxides such as tetracyclohexyl titanate, tetraphenyl titanate, and tetrabenzyl titanate, titanium oxides obtained by hydrolysis of titanium alkoxides, titanium obtained by hydrolysis of mixtures of titanium alkoxides and silicon alkoxides and/or zirconium alkoxides. -Silicon and/or zirconium composite oxide, titanium acetate, titanium oxalate, potassium titanium oxalate, sodium titanium oxalate, potassium titanate, sodium titanate, titanic acid-aluminum hydroxide mixture, titanium chloride, titanium chloride-chloride Examples include aluminum mixtures, titanium bromide, titanium fluoride, potassium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, ammonium hexafluorotitanate, and titanium acetylacetonate.

The radically polymerizable group introduced into the radically polymerizable group-introduced polymer is not particularly limited, but includes, for example, ethylenically unsaturated bonds other than those mentioned above, (meth)acryloyl group, maleimide group, vinyl group, etc. However, from the viewpoint of production costs, among others, a (meth)acryloyl group is preferable.

Examples of the radically polymerizable group-introduced polymer include, but are not limited to, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and the like.

Urethane (meth)acrylate is not particularly limited, but can be obtained, for example, by an addition reaction between a polyol, a diisocyanate, and a (meth)acrylate having a hydroxyl group. Specific examples of the polyisocyanate and polyol constituting the urethane (meth)acrylate are as follows.

Examples of polyisocyanates include, but are not limited to, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and those obtained by hydrogenating aromatic isocyanates among these diisocyanates. Diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, or polysaccharides obtained by polymerizing diisocyanates. Examples include isocyanates.

As the polyol, the polyols mentioned above can be used.

Epoxy (meth)acrylate is not particularly limited, but can be obtained, for example, by an addition reaction between polyglycidyl ether and (meth)acrylic acid. Examples of the polyglycidyl ether include, but are not limited to, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, and the like. It will be done.

Polyester (meth)acrylate is not particularly limited, but can be obtained, for example, by acryloylating the terminal end of a product obtained by a dehydration condensation reaction using a polycarboxylic acid and a polyol.

The polycarboxylic acid used in the dehydration condensation reaction is not particularly limited, but examples include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, and isophthalic acid. , terephthalic acid and the like. These polycarboxylic acids may be acid anhydrides.

Further, as the polyol used in the dehydration condensation reaction, the above-mentioned polyols can be used.

Furthermore, in this embodiment, maleimide compounds, prepolymers of these maleimide compounds, prepolymers of maleimide compounds and amine compounds, and the like may be used as the radical curable resin. Examples of maleimide compounds include, but are not limited to, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane. , bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane. It will be done. These may be used alone or in combination of two or more.

The content of the radical curable resin is 10 to 99.99% by mass, preferably 20 to 99.99% by mass, and more preferably 40 to 99.99% by mass based on the total amount of the curable resin composition. %, more preferably 60 to 99.99% by mass, even more preferably 80 to 99.99% by mass.

1.4. Other components In the curable resin composition of the present embodiment, other components include, but are not particularly limited to, an epoxy resin, a cyanate ester compound, a BT resin, an ester structure derived from a phenol group, and an aromatic carboxylic acid group. It may contain a compound having the following. Moreover, these components may be included as copolymerization components of the radical curable resin of this embodiment. The above components may be used alone or in combination of two or more.

Epoxy resins are not particularly limited, but include, for example, phenolphenylaralkyl novolak epoxy resins, phenolbiphenylaralkyl epoxy resins, naphthol aralkyl epoxy resins, anthraquinone epoxy resins, polyoxynaphthylene epoxy resins, and bisphenol A epoxy resins. Resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , aralkyl novolac type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, compounds with epoxidized double bonds such as glycidyl amine, glycidyl ester, or butadiene, and hydroxyl group-containing silicone resins obtained by reaction with epichlorohydrin. and halides thereof. These may be used alone or in combination of two or more.

Examples of cyanate ester compounds include, but are not limited to, naphthol aralkyl cyanate ester compounds, novolac cyanate esters, phenolbiphenylaralkyl cyanate ester compounds, and bis(3,5-dimethyl 4-cyanatophenyl). Methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4- dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4' -dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, 2,2-bis(4-cyanatophenyl)propane, poly Methylene polyphenyl polyisocyanate, m-tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate (1,3-bis(isocyanatomethyl)cyclohexane), isophorone diisocyanate, norbornene diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated methylene bisphenylene diisocyanate, 1 , 4-cyclohexane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, trifunctional isocyanate having an isocyanurate ring obtained by trimerizing a bifunctional isocyanate compound, and the like. These may be used alone or in combination of two or more.

BT resin is a prepolymer obtained by heating and mixing a cyanate ester compound and a maleimide compound without a solvent or in an organic solvent such as methyl ethyl ketone, N-methyl pyrodrine, dimethyl formamide, dimethyl acetamide, toluene, or xylene. It is. Here, as the cyanate ester compound and the maleimide compound, those described above can be used. These may be used alone or in combination of two or more.

The compound having an ester structure derived from a phenol group and an aromatic carboxylic acid group is not particularly limited, but for example, a compound having one phenolic hydroxyl group (a1), a compound having two or more phenolic hydroxyl groups (a2) and an active ester resin (I) using as a reaction raw material a compound selected from aromatic polycarboxylic acids or acid halides thereof (a3), compounds having two or more phenolic hydroxyl groups (b1), aromatic monocarboxylic acids or An active ester resin (II) using a compound selected from the acid halide (b2) and an aromatic polycarboxylic acid or the acid halide (b3) as a reaction raw material is exemplified. For specific examples of these compounds, reference can be made to International Publication No. 2020/003824. These may be used alone or in combination of two or more.

In addition, the curable resin composition of the present embodiment may optionally contain other components such as, but not limited to, a modified silicone oil, a heat stabilizer, an antioxidant, a curing agent, and a curing accelerator. May contain. The above components may be used alone or in combination of two or more.

Examples of the modified silicone oil include those having a chain-like siloxane skeleton and having groups other than hydrogen or hydrocarbon groups in the molecular structure. Examples of the modifying group include epoxy group, amino group, hydroxyl group, methacrylic group, mercapto group, carboxy group, alkoxy group, and silanol group. These may be used alone or in combination of two or more.

Examples of the heat stabilizer include, but are not particularly limited to, phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Specifically, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, triotadecyl phosphite, Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4 -Methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di- tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4, Examples include tetrakis 4'-biphenylene diphosphinic acid (2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like. These may be used alone or in combination of two or more.

Antioxidants include, but are not particularly limited to, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene. Glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxy) phenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di- tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, 4,4'-biphenylene diphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4) -hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane and the like. These may be used alone or in combination of two or more.

The curing agent is not particularly limited, but includes, for example, polyfunctional phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac resin; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride and acid anhydrides such as maleic anhydride.

Examples of the curing accelerator include, but are not limited to, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt (II) bisacetylacetonate, cobalt (III) trisacetylacetonate, and zinc (II). ) Organometallic salts and organometallic complexes such as acetylacetonate and iron (III) acetylacetonate, imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium Salt is an example.
These may be used alone or in combination of two or more.

The curable resin composition may further contain a radical polymerization initiator other than compound A, if necessary. Examples of such radical polymerization initiators include, but are not particularly limited to, organic peroxide initiators that initiate curing upon heating, and ultraviolet initiators that initiate curing upon irradiation with light.

Examples of organic peroxide initiators include, but are not limited to, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; and peroxy esters such as t-butyl peroxybenzoate. ; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide; and the like.

Examples of the ultraviolet initiator include, but are not limited to, benzophenones such as benzophenone, benzyl, and methyl orthobenzoyl benzoate; benzoin ethers such as benzoin alkyl ether; benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy-2 - Acetophenones such as methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone; thioxanthone such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Can be mentioned.

The curable resin composition may further contain fillers such as reinforcing base materials and inorganic fillers. The inorganic filler is not particularly limited as long as it is commonly used in the industry, but examples include silica such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum hydroxide, heat-treated aluminum hydroxide ( Metal hydroxides such as aluminum hydroxide (heat treated to reduce some of the crystallization water), magnesium hydroxide and boehmite; nitride compounds such as aluminum nitride and boron nitride; molybdenum such as molybdenum oxide and zinc molybdate Compounds: Zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (fine glass powders such as E glass and D glass), hollow glass, spherical Examples include glass, titanium oxide, silicone rubber, and silicone composite powder. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and the like. One kind of filler may be used alone, or two or more kinds of fillers may be used in combination.

The curable resin composition may contain a silane coupling agent and a wetting and dispersing agent in addition to the filler. Inclusion of these components tends to improve the dispersibility of the filler, especially the inorganic filler, and further improve the adhesive strength between the resin and the filler.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent that is generally used for surface treatment of inorganic materials, but examples include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ- Aminosilane-based silane coupling agents such as aminopropyltrimethoxysilane; Epoxysilane-based silane coupling agents such as γ-glycidoxypropyltrimethoxysilane; Vinylsilane-based silane coupling agents such as γ-methacryloxypropyltrimethoxysilane ; Cationic silane-based silane coupling agent such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; Phenylsilane-based silane coupling agent; p-styryltrimethoxysilane, p - Styrylsilane coupling agents such as styryltriethoxysilane, p-styrylmethyldimethoxysilane, p-styrylmethyldiethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc. etc.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, Disperbyk-110, 111, 180, 161, BYK-W996, W9010 manufactured by Big Chemie Japan Co., Ltd. , W903 and the like. These silane coupling agents and wetting and dispersing agents may be used alone or in combination of two or more.

Furthermore, the curable resin composition of this embodiment may contain a solvent as necessary. When the curable resin composition contains an organic solvent, the viscosity at the time of preparation of the curable resin composition tends to decrease, and the handling properties tend to improve. The solvent is not particularly limited as long as it can dissolve at least one component in the curable resin composition. Specific examples include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol methyl ether and its acetate. One type of solvent may be used alone, or two or more types may be used in combination.

1.5. Method for Preparing Curable Resin Composition The method for preparing the curable composition of this embodiment is not particularly limited, but for example, compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain. Examples include a method of mixing the radical curable resin, and other components as necessary, and sufficiently stirring the components so that each component is uniformly mixed.

2. Cured Product The cured product of this embodiment preferably has a dielectric loss tangent (10 GHz) of 0.006 or less. Normally, radical curable resins having a dielectric loss tangent (10 GHz) of 0.006 or less of the cured product are preferably used in substrate applications that are electronic materials. By containing 0.01 to 20% by mass of Compound A, it is possible to prevent the deterioration of the dielectric loss tangent caused by the radical polymerization initiator, thereby achieving a cure with a dielectric loss tangent (10 GHz) of 0.006 or less. can get things.

Further, the curing temperature of the curable resin composition of this embodiment is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. In this embodiment, since the curing temperature of Compound A used as a radical polymerization initiator is relatively low, the curable resin composition can be cured at the above curing temperature.

Note that the method of curing the curable resin composition of this embodiment is not particularly limited, and can be appropriately selected such as thermal curing and photocuring depending on the type of resin, etc., but as described above, the method of curing the curable resin composition of this embodiment Since the curing temperature of the curable resin composition is suitably carried out at 200°C or less, curing can be started at a relatively low temperature, so from the viewpoint of energy efficiency, equipment construction, cost, etc. Curing is preferred. In addition, when curing the curable resin composition, the resin composition may be dissolved in a solvent, mixed, dried, and then cured so that each component is mixed uniformly.

3. Applications Applications of the curable resin composition of the present embodiment and its cured product are not particularly limited, and include, for example, applications for substrates that are electronic materials. Specifically, examples include mold resin, rigid substrate, resin-coated copper foil, underfill material, and build-up film.

Hereinafter, the present invention will be explained in more detail using Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

1. Preparation of Resin A 137 g of 1,4-cyclohexanedimethanol, 183 g of diphenyl carbonate, and 0.0097 g of tetra-n-butyl titanate were placed in a 500 ml separable flask, and the temperature was gradually raised and the pressure reduced while stirring under a nitrogen flow. Finally, polymerization was carried out at 230° C. and 0.1 kPa or less. After cooling to room temperature, 9.3 g of maleic anhydride was added, and the temperature was raised to 200° C. and maintained until no distilled water came out. Thereafter, the pressure was gradually reduced to 13 kPa, and the pressure was maintained for 30 minutes to perform polymerization, thereby obtaining radical curable resin A. The number average molecular weight of radical curable resin A was 5,000.

2. Preparation of cured product <Example 1>
Spiroglycol diacrylate was put into a mold with a thickness of 1 mm, sandwiched between Afflex film (manufactured by AGC Corporation) and a SUS plate, and then put into a vacuum press heated at 160°C. After the pressure was reduced to 10 ⁻² kPa, the pressure was gradually pressed to 0.6 MPa, and after heating for 30 minutes, it was taken out and slowly cooled. After slow cooling, the cured resin composition was extracted from the mold. The extracted cured product was cut into a 0.8 mm width to prepare a bar-shaped sample. After drying the cut sample in a vacuum dryer at 70° C. for one day, the dielectric constant and dielectric loss tangent were measured. Note that in this embodiment, the dielectric constant means relative dielectric constant.

<Comparative example 1>
A cured product of tricyclodecane dimethanol dimethacrylate alone was prepared in the same manner as above except that spiroglycol diacrylate was changed to tricyclodecane dimethanol dimethacrylate.

<Comparative example 2>
Perbutyl P (α, α'-Di (t-butylperoxy) diisopropylbenzene, manufactured by NOF Corporation) was added in amounts of 3 parts by mass, 5 parts by mass, and 7 parts by mass to resin A, dissolved in toluene, and 20 wt. % of each solution was obtained. Thereafter, it was placed in a vacuum dryer and dried at room temperature for 48 hours and at 60° C. for 3 hours to remove toluene. The resin composition after toluene removal was put into a mold with a thickness of 1 mm, sandwiched between an Afflex film (manufactured by AGC Corporation) and a SUS plate, and then put into a vacuum press machine heated to 200°C. After the pressure was reduced to 10 ⁻² kPa, the pressure was gradually pressed to 0.6 MPa, and after heating for 90 minutes, it was taken out and slowly cooled. After slow cooling, the cured products of the resin compositions were extracted from the molds to obtain three types of cured products having different contents of perbutyl P.

<Example 2>
10 g of the resin A prepared above and 0.3 g of spiroglycol diacrylate were dissolved in toluene to prepare a 20 wt % solution. Thereafter, the solution was put into a vacuum dryer and dried at room temperature for 48 hours and at 60° C. for 3 hours to remove toluene. The resin composition after toluene removal was put into a mold with a thickness of 1 mm, sandwiched between an Afflex film (manufactured by AGC Corporation) and a SUS plate, and then put into a vacuum press machine heated to 200°C. After the pressure was reduced to 10 ⁻² kPa, the pressure was gradually pressed to 0.6 MPa, and after heating for 90 minutes, it was taken out and slowly cooled. After slow cooling, the cured product of Example 2 was obtained by extracting the cured product of the resin composition from the mold.

<Example 3 and Comparative Examples 3 to 5>
Cured products of Example 3 and Comparative Examples 3 to 5 were obtained in the same manner as in Example 2, except that the type and composition of the radical polymerization initiator and radical curable resin were changed based on Table 2. . As the maleimide resin in Table 2, BMI-5100 (Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used.

3. Evaluation method 3.1. Curing temperature Using DSC/TA-50WS manufactured by Shimadzu Corporation, about 10 mg of the cured products obtained in Example 1 and Comparative Examples 1 and 2 was placed in an aluminum non-sealed container, and nitrogen gas was added. (30 ml/min) In an air flow, the temperature was raised to 300° C. at a temperature increase rate of 20° C./min. The peak top when heat generation occurred was taken as the curing temperature. The results are shown in Table 1.

3.2. Dielectric Constant and Dielectric Dissipation Tangent The cured products obtained in Examples 1 to 3 and Comparative Examples 1 and 3 to 5 were each cut into a 0.8 mm width to prepare rod-shaped samples. After drying the cut samples in a vacuum dryer at 70° C. for one day, the dielectric constant and dielectric loss tangent of each sample at 10 GHz were measured using a cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). The results are shown in Tables 1 and 2.

In addition, regarding Comparative Example 2, each of the three types of cured products obtained above was cut out into a width of 0.8 mm to prepare each rod-shaped sample. After drying the cut samples in a vacuum dryer at 70° C. for one day, the dielectric constant and dielectric loss tangent of each sample at 10 GHz were measured using a cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). From the same values, calculate the proportional formula between the content of perbutyl P, the dielectric constant, and the dielectric loss tangent, and extrapolate so that the content ratio of perbutyl P becomes 100%. and the dielectric loss tangent were calculated. The results are shown in Table 1.

3.3. Residual Curing Using the cured products obtained in Examples 2 and 3 and Comparative Examples 3 and 4 as samples, approximately 10 mg of the samples were placed in an aluminum non-sealed container using a Shimadzu DSC/TA-50WS, and nitrogen The temperature was raised to 300° C. at a temperature increase rate of 20° C./min in a gas flow (30 ml/min), and the remaining cure was measured and evaluated using the following evaluation criteria. The results are shown in Table 2.
[Evaluation criteria]
○: No fever occurred.
×: Heat generation occurred.

Claims (10)

A compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain;
A radical curable resin;
The content of the compound A is 0.01 to 20% by mass based on the total amount of the curable resin composition,
The content of the radical curable resin is 10 to 99.99% by mass based on the total amount of the curable resin composition.
Curable resin composition. The compound A has a spiro ring skeleton,
At least one ring structure constituting the spiro ring skeleton has the dioxane skeleton,
The curable resin composition according to claim 1. The spiro ring skeleton has a spiro-fused skeleton of two dioxane skeletons,
The curable resin composition according to claim 2. the compound A is spiroglycol acrylate or spiroglycol diacrylate;
The curable resin composition according to claim 1. The compound A has a dispiro ring skeleton,
At least one ring structure constituting the dispiro ring skeleton has the dioxane skeleton,
The curable resin composition according to claim 1. The dispiro ring skeleton has a skeleton in which two dioxane skeletons are each spiro-fused to a cyclohexane skeleton,
The curable resin composition according to claim 5. The radical curable resin contains one or more functional groups selected from the group consisting of an ethylenically unsaturated bond, a (meth)acryloyl group, a maleimide group, and a vinyl group.
The curable resin composition according to any one of claims 1 to 6. A cured product obtained by curing the curable resin composition according to claims 1 to 6,
The dielectric loss tangent (10GHz) is 0.006 or less,
cured product. The curing temperature is 200°C or less,
The curable resin composition according to claim 7. As a radical polymerization initiator,
Use of compound A having a dioxane skeleton and a (meth)acryloyl group at at least one end of the molecular chain.