CN107663273B - Organosilicon compound, method for producing same, and curable composition - Google Patents
Organosilicon compound, method for producing same, and curable composition Download PDFInfo
- Publication number
- CN107663273B CN107663273B CN201710614721.5A CN201710614721A CN107663273B CN 107663273 B CN107663273 B CN 107663273B CN 201710614721 A CN201710614721 A CN 201710614721A CN 107663273 B CN107663273 B CN 107663273B
- Authority
- CN
- China
- Prior art keywords
- group
- carbon atoms
- formula
- unsubstituted
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to an organosilicon compound, a method for producing the same, and a curable composition, and provides an organosilicon compound effective as a resin modifier for high-frequency substrate materials, a method for producing the same, and a curable composition containing the same. An organosilicon compound characterized by being represented by the average structural formula (i) (wherein X represents an n-valent organic group containing a polyphenylene ether structure, R 1 Independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, R 2 Independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, A 1 Represents a single bond or a divalent linking group containing a hetero atom, A 2 Represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which is unsubstituted or substituted, and which does not contain a hetero atom, m is a number of 1 to 3, and n is a number of 1 to 10. )
Description
Technical Field
The present invention relates to an organosilicon compound, a method for producing the same, and a curable composition, and more particularly, to an organosilicon compound having a polyphenylene ether structure and a hydrolyzable group in the molecule, a method for producing the same, a curable composition containing the organosilicon compound, and a cured article thereof.
Background
Silane coupling agents are compounds that contain both a portion having reactivity with inorganic substances (hydrolyzable group bonded to Si atom) and a portion having reactivity and solubility with organic substances in 1 molecule, and are widely used as modifiers for composite resins because they function as an adhesion promoter at the interface between inorganic substances and organic substances.
Further, it is known that a polyphenylene ether compound is highly heat resistant and is excellent in dielectric characteristics such as a dielectric constant and a dielectric loss tangent, and particularly excellent in dielectric characteristics in a high frequency band (high frequency region) from the MHz band to the GHz band, that is, high frequency characteristics.
Therefore, in recent years, it has been considered that the polyphenylene ether compound is suitably used as a molding material for high frequency signals. Specifically, as a component of a substrate material used for a base material (copper-clad laminate) constituting a printed wiring board provided in an electronic device utilizing an electric signal in a high-frequency region, a combination use with an epoxy resin or the like has been studied.
In such applications, since an electric signal in a high frequency range tends to be easily attenuated in a wiring circuit, an electronic circuit board having good transmission characteristics is considered to be necessary.
In order to obtain an electronic circuit board having excellent transmission characteristics, it is effective to use an insulating resin material having a small dielectric loss tangent such as a polyphenylene ether compound, and to smooth the surface of a conductor (metal wiring such as a copper foil) and reduce the skin resistance by reducing the thickness and thickness.
However, since the conventional copper-clad laminate ensures adhesion between the resin material and the copper foil by providing irregularities on the surface of the copper foil to exhibit anchor effect, there is a problem that the anchor effect is weakened and the adhesion between the resin material and the copper foil is deteriorated if the surface of the copper foil is smoothed to obtain transmission characteristics as in the case of the above-mentioned high-frequency substrate material.
Therefore, the use of a general silane coupling agent has been studied in order to improve the adhesion, but the adhesion is not yet sufficiently satisfied at present.
Further, patent document 1 discloses an alkoxysilyl group-containing silane-modified phenylene ether resin obtained by subjecting a 2-functional phenylene ether resin to a dealcoholization condensation reaction with an alkoxysilane partial condensate.
However, in the compound of patent document 1, the alkoxysilyl group having the highest reactivity and contributing to the improvement of the adhesion is consumed in the dealcoholization condensation reaction in the production method, and therefore the adhesion between the resin material and the copper foil is not sufficient.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2005-330324
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an organic silicon compound effective as a resin modifier for high-frequency substrate materials, a method for producing the same, and a curable composition containing the same.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a predetermined organic silicon compound having a polyphenylene ether structure and a hydrolyzable group in the molecule and a method for producing the same, and that a composition containing the organic silicon compound gives a cured product which can exhibit good copper foil adhesion, dielectric characteristics such as a dielectric constant and a dielectric loss tangent, and thus the present invention has been completed as a curable composition suitable for forming a material for a high-frequency substrate.
Namely, the present invention provides:
1. an organosilicon compound characterized by being represented by an average structural formula (i):
[ CHEM 1]
(wherein X represents an n-valent organic group containing a polyphenylene ether structure, and R 1 Independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, R 2 Independently of one another, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, A 1 Represents a single bond or a divalent linking group containing a hetero atom, A 2 Represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which is unsubstituted or substituted, and which does not contain a hetero atom, m is a number of 1 to 3, and n is a number of 1 to 10. )
An organosilicon compound represented by the average structural formula (1) or (2):
[ CHEM 2]
{ formula (II) wherein R 1 、R 2 、A 1 、A 2 And m represents the same meaning as above, R 3 Independently represent a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, R 4 Independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are independently a number of 1 to 100, c is a number of 0 or more and less than 2, and Z represents a linking group represented by the following formula (3).
[ CHEM 3 ]
[ (in the formula, R 4 The same meanings as above, and L represents a linking group selected from the following formulae (4) to (11). )
[ CHEM 4]
(in the formula, R 5 Independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 6 Independently of each other, each represents an alkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 12, and j represents a number of 1 to 1,000. )]}
3.1 or 2, wherein A is 1 -A 2 Represented by formula (12) or formula (13):
[ CHEM 5]
4.1 to 3, characterized in that the average structural formula (14) or (15)
[ CHEM 6 ]
(in the formula, R 3 、R 4 A, b and Z represent the same meanings as described above. )
A polyphenylene ether compound having a hydroxyl group represented by the formula (16)
[ CHEM 7 ]
(wherein R is 1 、R 2 、A 2 And m represents the same meaning as described above. )
A compound having an isocyanate group and an alkoxysilyl group,
5.1 to 3, characterized in that the average structural formula (14) or (15)
[ CHEM 8 ]
(in the formula, R 3 、R 4 A, b and Z represent the same meanings as described above. )
A polyphenylene ether compound having a hydroxyl group represented by the formula (17) is reacted with a compound having a functional group reactive with the hydroxyl group and an alkenyl group to obtain an alkenyl compound, and the alkenyl compound is reacted with a compound represented by the formula (17)
[ CHEM 9 ]
(formula (II)In, R 1 、R 2 And m represents the same meaning as described above. )
The silane compound represented by (a) is subjected to a hydrosilylation reaction,
6. a curable composition comprising an organosilicon compound according to any one of 1 to 3,
7.6A cured article obtained by curing the curable composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The organosilicon compound of the present invention has a polyphenylene ether structure and a highly reactive hydrolyzable group in the molecule, and has excellent dielectric properties such as copper foil adhesiveness, dielectric constant and dielectric loss tangent as compared with conventional silane coupling agents.
The composition containing the organosilicon compound of the present invention having such characteristics can be suitably used as a curable composition, particularly a curable composition for forming a high-frequency substrate material.
Detailed Description
The present invention will be specifically described below.
The organosilicon compounds of the invention are represented by the average structural formula (i).
[ CHEM 10 ]
Wherein X represents an n-valent organic group containing a polyphenylene ether structure, and R 1 Independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, R 2 Independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, A 1 Represents a single bond or a divalent linking group containing a hetero atom, A 2 Represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which is unsubstituted or substituted, and which does not contain a hetero atom, m is a number of 1 to 3, and n is a number of 1 to 10.
As R 1 And R 2 Alkyl group having 1 to 10 carbon atoms in a straight chainExamples of the cyclic or branched alkyl group include a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group, and a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
As R 1 And R 2 Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl group, α -naphthyl group, β -naphthyl group and the like.
Some or all of the hydrogen atoms of these groups may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom such as F, cl or Br, a cyano group or the like, and specific examples of such groups include a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group, a tolyl group, a xylyl group and the like.
Among these, as R 1 From the viewpoint of hydrolyzability, a linear alkyl group having 1 to 5 carbon atoms is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is further preferred.
On the other hand, as R 2 The alkyl group is preferably a linear alkyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
In addition, m is an integer of 1 to 3, preferably 2 to 3, and more preferably 3, from the viewpoint of reactivity.
As the above-mentioned A 1 Specific examples of the divalent linking group containing a hetero atom of (1), examples thereof include an ether bond (-O-), a thioether bond (-S-), and amino linkage (-NH-), sulfonyl linkage (-S (= O) 2 -), phosphinyl linkage (-P (= O) OH-), oxo linkage (-C (= O) -), thio linkage (-C (= S) -), ester linkage (-C (= O) O-), thioester linkage (-C (= O) S-), thiocarbonyl linkage (-C (= S) O-), dithioester linkage (-C (= S) S-), carbonate linkage (-OC (= O) O-), thiocarbonate linkage (-OC (= S) O-), and combinations thereof an amide bond (-C (= O) NH-), a thioamide bond (-C (= S) NH-), a urethane bond (-OC (= O) NH-), a thiourethane bond (-SC (= O) NH-), a thiourethane bond (-OC (= S) NH-), a dithiourethane bond (-SC (= S) NH-), a urea bond (-NHC (= O) NH-), a thiourea bond (-NHC (= S) NH-), and the like.
Among these, as A 1 Preferably an ether linkage (-O-) or urineAn alkyl linkage (-OC (= O) NH-).
On the other hand, as A 2 Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted and does not contain a hetero atom include alkylene groups such as methylene, ethylene, trimethylene, propylene, isopropylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecylmethylene, nonadecamethylene, and eicosylene; cycloalkylene groups such as cyclopentylene and cyclohexylene; arylene groups such as phenylene and α -, β -naphthylene.
Of these, trimethylene group and octamethylene group are preferred, and trimethylene group is more preferred.
X in the formula (i) represents an n-valent linking group containing a polyphenylene ether structure, and may have a linear structure, a branched structure, or a crosslinked structure.
The average of n per molecule is 1 to 10, preferably 1 to 5, more preferably 1 to 2. If n is less than 1, the reactivity is poor because of insufficient hydrolyzable groups. On the other hand, if n exceeds 10, the number of reaction sites increases excessively, and therefore the storage stability of the compound may deteriorate or cracks may easily occur in the cured product.
The X is not particularly limited as long as it is an n-valent linking group containing a polyphenylene ether structure, and in the present invention, a group represented by the following formula is particularly preferable in consideration of improvement of adhesion to a copper foil and dielectric characteristics.
[ CHEM 11 ]
Therefore, as the organic silicon compound of the present invention, an organic silicon compound having an average structural formula represented by formula (1) or formula (2) is preferable, and by using these compounds, more excellent copper foil adhesion and dielectric characteristics are exhibited.
[ CHEM 12 ]
In each of these formulae, R 1 、R 2 、A 1 、A 2 And m represents the same meaning as above, R 3 Independently represent a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, R 4 Independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are independently a number of 1 to 100, c is a number of 0 or more and less than 2, and Z represents a linking group represented by the following formula (3).
[ CHEM 13 ]
R is as defined above 4 The same meanings as above, and L represents a linking group selected from the following formulae (4) to (11).
[ CHEM 14 ]
R is as defined above 5 Independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 6 Independently of each other, each represents an alkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 12, and j represents a number of 1 to 1,000.
As R 3 And R 4 The alkyl group having 1 to 12 carbon atoms may be a linear, cyclic or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group and an n-propyl groupStraight-chain or branched alkyl groups such as isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
As R 3 And R 4 The alkoxy group having 1 to 12 carbon atoms may be any of linear, cyclic and branched alkoxy groups, and specific examples thereof include linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, and cycloalkoxy groups such as cyclopentoxy, cyclohexyloxy, cycloheptyloxy and cyclooctyloxy groups.
Some or all of the hydrogen atoms of these groups may be substituted with a halogen atom such as F, cl or Br, a mercapto group, a cyano group or the like, and specific examples of such groups include a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 3-mercaptopropyl group, a 2-cyanoethyl group or the like.
As R 3 And R 4 Examples of the halogen atom of (b) include F, cl and Br.
Among these, as R 3 From the viewpoint of ease of production, a methyl group and a methoxy group are preferable, and a methyl group is more preferable.
On the other hand, as R 4 The hydrogen atom, methyl group and methoxy group are preferable, and the hydrogen atom is more preferable.
A and b are each independently a number of 1 to 100, but from the viewpoint of copper foil adhesion and dielectric properties of the organosilicon compound, they are preferably 3 to 50, more preferably 5 to 20. When a and b are smaller than 1, good copper foil adhesion and dielectric properties may not be obtained, and when a and b are larger than 100, compatibility of the organic silicon compound with the organic resin may be deteriorated.
Further, in the present invention, the compound is represented by the formula-A 1 -A 2 A group, preferably a trimethylene group having a urethane bond (-OC (= O) NH-) represented by formula (12), a trimethylene group having a urethane bond (-OC (= O) NH-) represented by formula (13)A trimethylene group of an ether bond (-O-).
[ CHEM 15 ]
The weight average molecular weight of the organosilicon compound of the present invention is not particularly limited, and is preferably 500 to 5 ten thousand, more preferably 1,000 to 2 ten thousand, and further preferably 4,000 to 1 ten thousand, considering that workability is improved by setting the viscosity and the like of the curable composition containing the compound to an appropriate range, and sufficient copper foil adhesiveness and dielectric properties are imparted to the obtained cured product. The weight average molecular weight in the present invention is a polystyrene equivalent value obtained by Gel Permeation Chromatography (GPC).
Further, the organosilicon compound of the present invention can be used in a state containing a solvent.
The solvent is not particularly limited as long as it has the ability to dissolve the organosilicon compound represented by formula (i), and an aromatic solvent such as toluene or xylene is preferable from the viewpoint of solubility and volatility; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran, and toluene and xylene are more preferable among them.
The amount of the solvent added is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass, relative to 100 parts by mass of the organosilicon compound represented by the formula (i).
A in the organosilicon compound represented by the above formula (i) 1 The compound that is a urethane bond can be obtained by reacting a compound having a group containing a polyphenylene ether structure and a hydroxyl group in 1 molecule represented by formula (14) or formula (15) as an average structural formula with a compound having an isocyanate group and an alkoxysilyl group represented by formula (16) (hereinafter referred to as isocyanatosilane).
More specifically, a reaction of forming a urethane bond between the hydroxyl group of the compound represented by the average structural formula (14) or (15) and the isocyanate group of the isocyanatosilane is carried out.
[ CHEM 16 ]
(wherein R is 3 、R 4 A, b and Z are the same as described above. )
[ CHEM 17 ]
(wherein R is 1 、R 2 、A 2 And m is the same as described above. )
The compounds represented by the formulae (14) and (15) are commercially available, and examples of such commercially available products include PPO (trade Mark) SA120-100 and PPO (trade Mark) SA90-100 manufactured by SABIC Innovative Plastics.
On the other hand, specific examples of the isocyanatosilane represented by the formula (16) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyldimethylethoxysilane and the like.
Among these, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane are preferable, and 3-isocyanatopropyltrimethoxysilane is more preferable from the viewpoint of hydrolyzability.
The ratio of the reaction between the compound represented by formula (14) or formula (15) having a group having a polyphenylene ether structure and a hydroxyl group in 1 molecule and the isocyanatosilane represented by formula (16) is preferably 0.01 to 1.2mol, more preferably 0.1 to 1.1mol, and still more preferably 0.4 to 1mol, based on 1mol of the hydroxyl group in the compound represented by formula (14) or formula (15), in view of suppressing by-products during urethanization reaction and improving the storage stability and properties of the obtained organosilicon compound.
In addition, a catalyst for increasing the reaction rate can be used in the urethanization reaction.
The catalyst may be suitably selected from catalysts generally used in urethanization reactions, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin (II) bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, and the like.
The amount of the catalyst to be used may be a catalytic amount, and is usually 0.001 to 1% by mass based on the total amount of the compound represented by formula (14) or formula (15) and the isocyanatosilane represented by formula (16).
In the urethanization reaction, a solvent which does not react with the raw material to be used can be used.
Specific examples thereof include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane and cyclohexane; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as formamide, N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone, and ester solvents such as ethyl acetate, butyl acetate, γ -butyrolactone, and propylene glycol-1-monomethyl ether-2-acetate; ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane, and these may be used alone or in combination of 2 or more.
The reaction temperature in the urethane reaction is not particularly limited, but is preferably 25 to 90 ℃ and more preferably 40 to 80 ℃ in view of the suppression of side reactions such as allophanation while adjusting the reaction rate appropriately.
The reaction time is not particularly limited, and is usually 10 minutes to 24 hours.
Further, A in the organosilicon compound represented by the formula (i) 1 The compound which is an ether bond can be prepared by reacting a compound having a polyphenylene ether structure-containing group and a hydroxyl group in 1 molecule represented by the above formula (14) or formula (15) as an average structural formula with a compound having a functional group reactive with the hydroxyl group and an alkenyl group as a1 st stage to prepare an alkenyl compound, and then reacting the 1 st stage with the compound having a functional group reactive with the hydroxyl group and an alkenyl group as a 2 nd stageThe alkenyl compound obtained in the above paragraph is reacted with a silane compound represented by formula (17).
More specifically, in the 1 st stage, a functional group reactive with a hydroxyl group is reacted with a hydroxyl group, a compound having an average structural formula represented by formula (14) or (15) is coupled with a compound having an alkenyl group using an ether bond, and in the 2 nd stage, the alkenyl compound obtained in the 1 st stage and a silane compound represented by formula (17) are hydrosilylated in the presence of a catalyst containing a platinum compound, and a hydrosilyl group is added to the alkenyl group to form a carbon-silicon bond.
[ CHEM 18 ]
(in the formula, R 1 、R 2 And m is the same as described above. )
The functional group of the compound having a functional group reactive with a hydroxyl group and an alkenyl group used in the 1 st stage is not particularly limited as long as it is a functional group selectively reactive with a hydroxyl group, and examples thereof include a halogen atom, a mesylate group, a triflate group, a p-toluenesulfonate group and the like, preferably a halogen atom, more preferably a chlorine atom, a bromine atom and an iodine atom.
Specific examples of the compound having a halogen atom and an alkenyl group (hereinafter referred to as an alkenyl halide compound) include alkenyl chloride compounds such as allyl chloride, methallyl chloride, butenyl chloride, pentenyl chloride, hexenyl chloride, heptenyl chloride, octenyl chloride, nonenyl chloride and the like; alkenyl bromide compounds such as allyl bromide, methallyl bromide, butenyl bromide, pentenyl bromide, hexenyl bromide, heptenyl bromide, octenyl bromide, nonenyl bromide and the like; alkenyl iodide compounds such as allyl iodide, methallyl iodide, butenyl iodide, pentenyl iodide, hexenyl iodide, heptenyl iodide, octenyl iodide, nonenyl iodide and the like.
Among these, from the viewpoint of reactivity and availability, allyl chloride, hexenyl chloride, octenyl chloride, allyl bromide, and allyl iodide are preferable, allyl chloride, octenyl chloride, and allyl bromide are more preferable, and allyl bromide is even more preferable.
The reaction in the 1 st stage can be carried out by a conventionally known general method, and for example, a synthesis method of an asymmetric ether (Williams synthesis, williams ether synthesis) or the like by a nucleophilic substitution reaction of a hydroxyl group with an alkenyl halide compound or the like in the presence of a basic compound can be used.
In this case, the reaction ratio of the compound represented by formula (14) or formula (15) and the alkenyl halide compound is not particularly limited, but if considering further reduction of unreacted raw materials and improvement of the storage stability and various characteristics of the obtained organosilicon compound, the halogen atom of the alkenyl halide compound is preferably 0.1 to 10mol, more preferably 0.2 to 5mol, and further preferably 0.4 to 1.2mol with respect to 1mol of the hydroxyl group of the compound represented by formula (14) or formula (15).
As the basic compound, various basic compounds used in the williamson synthesis method can be generally used, and any basic compound can be used as long as it does not react with a compound other than the hydroxyl group of the compound represented by formula (14) or formula (15).
Specific examples thereof include alkali metals such as metallic sodium and metallic lithium; alkaline earth metals such as calcium metal; alkali metal hydrides such as sodium hydride, lithium hydride, potassium hydride, and cesium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide and aqueous solutions thereof, and alkaline earth metal hydroxides such as barium hydroxide and calcium hydroxide and aqueous solutions thereof; alkali metal and alkaline earth alkoxides such as potassium tert-butoxide and sodium tert-butoxide; alkali metal and alkaline earth metal carbonates such as potassium carbonate, sodium carbonate, and calcium carbonate; alkali metal and alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; tertiary amines such as triethylamine, tributylamine, N-diisopropylethylamine, tetramethylethylenediamine, pyridine, and N, N-dimethyl-4-aminopyridine.
Among these, from the viewpoint of reaction efficiency, hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, and calcium hydroxide, or aqueous solutions thereof are preferred, and aqueous solutions of sodium hydroxide are more preferred.
The amount of the basic compound to be used is not particularly limited, but is preferably 0.5 to 20mol, more preferably 1 to 10mol, further preferably 2 to 8mol, based on 1mol of the hydroxyl group of the compound represented by formula (14) or formula (15), from the viewpoints of preventing the remainder of the raw material and the excess remainder of the basic compound, and improving the storage stability and various characteristics of the obtained organosilicon compound, if the etherification reaction is sufficiently performed.
In the etherification reaction, a solvent that does not react with the raw material used can be used.
Specific examples thereof include water; hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, cyclohexane and the like; aromatic solvents such as benzene, toluene and xylene; amide solvents such as formamide, N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone; ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; and nitrile solvents such as acetonitrile, and these may be used alone or in combination of 2 or more.
Among these, from the viewpoint of reaction efficiency, water, toluene, xylene, dimethylformamide, cyclopentylmethyl ether, and tetrahydrofuran are preferable, and a mixed solvent of water and toluene and a mixed solvent of water and xylene are more preferable.
The reaction temperature in the etherification reaction is not particularly limited, but is preferably 25 to 90 ℃, more preferably 40 to 80 ℃, and still more preferably 50 to 70 ℃ in view of the suppression of volatilization of the alkenyl halide compound while adjusting the reaction rate appropriately.
The etherification reaction is usually carried out under atmospheric pressure, and may be carried out under pressure in order to suppress volatilization of the alkenyl halide compound, increase the reaction rate, and the like.
The reaction time is not particularly limited, and is usually 10 minutes to 24 hours.
In the etherification reaction, a catalyst is used to increase the reaction rate.
As the catalyst, a catalyst which does not react with a compound other than the hydroxyl group of the compound represented by formula (14) or formula (15) can be appropriately selected from catalysts which have been generally used in the williamson synthesis method.
Specific examples thereof include crown ethers such as 12-crown-4, 15-crown-5, 18-crown-6 and dibenzo-18-crown-6; quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, and the like; alkali metal halides such as potassium iodide and sodium iodide, which may be used alone or in combination of 2 or more.
Among these, from the viewpoint of reactivity and availability, 18-crown-6, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate and potassium iodide are preferable, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate and potassium iodide are more preferable, and tetrabutylammonium hydrogen sulfate is further preferable.
The catalyst can function as a phase transfer catalyst or activate an alkenyl halide compound to increase the reaction rate.
The amount of the catalyst to be used may be a catalytic amount, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, based on the total amount of the compound represented by formula (14) or formula (15) and the alkenyl halide compound.
Specific examples of the silane compound represented by the formula (17) used in the reaction with the alkenyl compound obtained in the stage 1 in the stage 2 include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane and the like, and from the viewpoint of hydrolyzability, trimethoxysilane and triethoxysilane are preferable, and trimethoxysilane is more preferable.
The catalyst containing a platinum compound used in the hydrosilylation in the 2 nd stage is not particularly limited, and specific examples thereof include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene or xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakis (triphenylphosphine) platinum, dichlorobis (triphenylphosphine) platinum, dichlorodiacetonitrile platinum, dichlorobis benzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina, platinum-silica, and other supported catalysts.
Among these, from the viewpoint of selectivity, a 0-valent platinum complex is preferable, and a toluene or xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferable.
The amount of the catalyst containing a platinum compound used is not particularly limited, and from the viewpoint of reactivity and productivity, it is preferable that the platinum atom contained is 1 × 10 with respect to 1mol of the silane compound represented by the formula (17) -7 ～1×10 -2 The amount of mol is more preferably 1X 10 -7 ～1×10 -3 The amount of mol.
In addition, in order to improve the reactivity of hydrosilylation, a co-catalyst may be used. As the co-catalyst, those commonly used in hydrosilylation can be used, and in the present invention, ammonium salts of inorganic acids, acid amide compounds, and carboxylic acids are preferable.
Specific examples of the ammonium salt of the inorganic acid include ammonium chloride, ammonium sulfate, ammonium sulfamate, ammonium nitrate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, diphosphonite, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfide, ammonium borate, ammonium borofluoride and the like, among which ammonium salts of inorganic acids having a pKa of 2 or more are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.
Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalic diamide, palmitamide, and stearamide.
Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, lactic acid, and glycolic acid, and of these, formic acid, acetic acid, and lactic acid are preferable, and acetic acid is more preferable.
The amount of the cocatalyst to be used is not particularly limited, but is preferably 1 × 10 to 1mol of the silane compound represented by formula (17) from the viewpoints of reactivity, selectivity, cost, and the like -5 ～1×10 -1 mol, more preferably 1X 10 -4 ～5×10 - 1 mol。
The hydrosilylation reaction is carried out in the absence of a solvent, but a solvent may be used.
Specific examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N, N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform, and these solvents may be used alone in 1 kind or in a mixture of 2 or more kinds.
The reaction temperature in the hydrosilylation reaction is not particularly limited, and the reaction can be carried out under heating from 0 ℃ but is preferably 0 to 200 ℃.
In order to obtain an appropriate reaction rate, it is preferable to react the reaction mixture under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ℃, and still more preferably 40 to 90 ℃.
The reaction time is not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, and more preferably 1 to 20 hours.
The curable composition of the present invention contains an organosilicon compound represented by formula (i).
The organosilicon compound represented by the formula (i) of the present invention is derived from the structure of the organosilicon compound, and improves the adhesion and dielectric properties of a copper foil of a cured product obtained using a curable composition containing the organosilicon compound, as compared with conventional organosilicon compounds.
The content of the organosilicon compound in the curable composition of the present invention is not particularly limited, but is preferably about 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass in the curable composition. When the organosilicon compound contains a solvent, the above content means that a nonvolatile component of the solvent is not included.
The curable composition of the present invention preferably contains an organic resin.
The organic resin is not particularly limited, and specific examples thereof are appropriately selected from epoxy resins, phenol resins, polycarbonate-based and polycarbonate-based blends, acrylic resins, polyester resins, polyamide resins, polyimide resins, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride resins, polystyrene resins, polyphenylene ether resins, blends of polystyrene and polyphenylene ether, cellulose acetate butyrate, polyethylene resins, and the like, depending on the application, and if considering use as a substrate material for a printed wiring board in an electronic device utilizing an electric signal in a high frequency region, epoxy resins, polyphenylene ether resins, or blends thereof are preferable.
In this case, an appropriate curing agent can be blended according to the organic resin to be used, and for example, in the case of using an epoxy resin, a curing agent such as an imidazole compound can be blended.
Further, as the crosslinking component, for example, a cyanate ester compound and the like can be appropriately blended, and further, various additives such as an adhesion improving agent, an ultraviolet absorber, a storage stability improving agent, a plasticizer, a filler, and a pigment can be added according to the purpose of use.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
In the following, the viscosity is a measured value at 25 ℃ using a B-type rotational viscometer, the molecular weight is a weight average molecular weight in terms of polystyrene determined by GPC (gel permeation chromatography), and the nonvolatile content is a measured value obtained by a heat residue method after heating and drying at 105 ℃ for 3 hours on an aluminum dish.
[1] Synthesis of organosilicon Compounds
[ examples 1 to 1]Synthesis of organosilicon Compound 1
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 40g of PPO (trademark) SA120-100 (manufactured by SABIC Innovative Plastics, inc.), 40g of toluene 110g and 0.05g of dioctyltin dilaurate, and heated to 80 ℃. 7.6g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ℃ for 2 hours. It was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared, and instead, an absorption peak derived from a urethane bond was generated, and the reaction was considered to be completed.
The resulting reaction product was a brown transparent liquid having a weight average molecular weight of 6,700 and a viscosity of 23mm 2 (s) nonvolatile components in an amount of 34% by mass.
Examples 1 to 2]Synthesis of organosilicon Compound 2
The synthesis was carried out in the same manner as in example 1-1, except that the amount of 3-isocyanatopropyltriethoxysilane was changed to 9.2 g.
The obtained reaction product was a brown transparent liquid, and had a weight-average molecular weight of 6,800 and a viscosity of 30mm 2 (s) 30% by mass of a nonvolatile component.
[ examples 1 to 3]Synthesis of organosilicon Compound 3
The synthesis was carried out in the same manner as in example 1-1, except that the amount of toluene was changed to 120g, and the amount of 3-isocyanatopropyltrimethoxysilane was changed to 11.1 g.
The obtained reaction product was a brown transparent liquid, and had a weight-average molecular weight of 5,300 and a viscosity of 21mm 2 (s) nonvolatile matter content of 29 mass%.
[ examples 1 to 4]Synthesis of organosilicon Compound 4
The synthesis was carried out in the same manner as in example 1-1, except that the amount of 3-isocyanatopropyltrimethoxysilane was changed to 5.6 g.
The obtained reaction product was a brown transparent liquid, and had a weight-average molecular weight of 4,200 and a viscosity of 12mm 2 (s) 30% by mass of a nonvolatile component.
Examples 1 to 5]Synthesis of organosilicon Compound 5
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 40g of PPO (trademark) resin powder (manufactured by SABIC Innovative Plastics, ltd.), 110g of toluene and 0.05g of dioctyltin dilaurate, and heated to 80 ℃. 0.5g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ℃ for 2 hours. Then, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared, and instead, an absorption peak derived from a urethane bond was generated, and the reaction was considered to be completed.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 102,000 and a viscosity of 1,200mm 2 (s) nonvolatile components in an amount of 28% by mass.
[ examples 1 to 6]Synthesis of organosilicon Compound 6
A polyphenylene ether was obtained by rearrangement by distribution of non 640-111 (manufactured by SABIC Innovative Plastics) according to the method described in example "PPE-3" of Japanese patent application laid-open No. 2015-086329.
In a 200mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 40g of the polyphenylene ether, 110g of toluene and 0.05g of dioctyltin dilaurate which were obtained in the above-described rearrangement by distribution were charged, and heated to 80 ℃. 27.8g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ℃ for 2 hours. Then, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared, and instead, an absorption peak derived from a urethane bond was generated, and the reaction was considered to be completed.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 6,200 and a viscosity of 49mm 2 (s) nonvolatile components in an amount of 30% by mass.
Examples 1 to 7]Synthesis of organosilicon Compound 7
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 40g of polyphenylene ether, 110g of toluene and 0.05g of dioctyltin dilaurate which had been rearranged in examples 1 to 6, and heated to 80 ℃. 13.9g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ℃ for 2 hours. Then, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and instead an absorption peak derived from the urethane bond was generated, and the reaction was considered to be completed.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 5,000 and a viscosity of 35mm 2 (s) 30% by mass of a nonvolatile component.
Examples 1 to 8]Synthesis of organosilicon Compound 8
[ stage 1]
A300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 50g of PPO (trade name) SA120-100 (manufactured by SABIC Innovative Plastics, ltd.), 120g of toluene, 0.56g of tetrabutylammonium hydrogen sulfate and 37.6g of a 30% aqueous solution of sodium hydroxide, and heated to 60 ℃. 5.7g of allyl bromide was added dropwise thereto, and the mixture was heated and stirred at 60 ℃ for 6 hours. Then, the mixture was allowed to stand, the aqueous layers separated by the two layers were separated, the organic layer was washed with water until the mixture became neutral, and the organic layer was concentrated under reduced pressure (80 ℃ C., 5 mmHg) to remove volatile components, whereby the corresponding alkenyl compound was obtained as a brown solid.
[ stage 2]
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 30g of the alkenyl compound obtained in the above-mentioned stage 1, 70g of toluene, and 0.08g (5.0X 10 in terms of platinum atom per 1mol of trimethoxysilane) of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (obtained in the above-mentioned step 1) -5 mol) of a reaction mixture, 3.5g of trimethoxysilane was charged at an internal temperature of 75 to 85 ℃ and then stirred at 80 ℃ for 1 hour.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 6,000 and a viscosity of 15mm 2 (s) nonvolatile components of 31 mass%.
Examples 1 to 9]Synthesis of organosilicon Compound 9
[ stage 1]
A300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 50g of PPO (trade name) SA120-100 (manufactured by SABIC Innovative Plastics, ltd.), 120g of toluene, 0.56g of tetrabutylammonium iodide and 37.6g of a 30% aqueous solution of sodium hydroxide, and heated to 60 ℃. 6.9g of octenyl chloride was added dropwise thereto, and the mixture was heated and stirred at 60 ℃ for 6 hours. Then, the mixture was allowed to stand, the aqueous layers separated by the two layers were separated, the organic layer was washed with water until the mixture became neutral, and the organic layer was concentrated under reduced pressure (80 ℃ C., 5 mmHg) to remove volatile components, whereby the corresponding alkenyl compound was obtained as a brown solid.
[2 nd stage ]
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 30g of the alkenyl compound obtained in the above-mentioned stage 1, 70g of toluene, and 0.08g (5.0X 10 in terms of platinum atom per 1mol of trimethoxysilane) of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (obtained in the above-mentioned step 1) -5 mol) and 0.003g of acetic acid, 3.4g of trimethoxysilane was charged at an internal temperature of 75 to 85 ℃ and then stirred at 80 ℃ for 1 hour.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 6,100 and a viscosity of 17mm 2 (s) nonvolatile components in an amount of 30% by mass.
Examples 1 to 10]Synthesis of organosilicon Compound 10
[ stage 1]
A300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 50g of PPO (trade name) SA90-100 (manufactured by SABIC Innovative Plastics, ltd.), 130g of toluene, 0.58g of tetrabutylammonium hydrogen sulfate and 54.1g of a 30% aqueous solution of sodium hydroxide, and heated to 60 ℃. 8.2g of allyl bromide was added dropwise thereto, and the mixture was heated and stirred at 60 ℃ for 6 hours. Then, the mixture was allowed to stand, the aqueous layers separated by the two layers were separated, the organic layer was washed with water until the mixture became neutral, and the organic layer was concentrated under reduced pressure (80 ℃ C., 5 mmHg) to remove volatile components, whereby the corresponding alkenyl compound was obtained as a brown solid.
[ stage 2]
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 40g of the alkenyl compound obtained in the above-mentioned stage 1, 60g of toluene, and 0.10g (5.0X 10 in terms of platinum atom per 1mol of trimethoxysilane) of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (obtained in the above-mentioned step 1) -5 mol) of a silane compound (I), 6.3g of trimethoxysilane was charged at an internal temperature of 75 to 85 ℃ and then stirred at 80 ℃ for 1 hour.
The obtained reaction product is brownClear liquid, weight average molecular weight 4,800, viscosity 13mm 2 (s) nonvolatile components of 31 mass%.
Examples 1 to 11]Synthesis of organosilicon Compound 11
[ stage 1]
A300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 50g of PPO (trade name) SA90-100 (manufactured by SABIC Innovative Plastics, ltd.), 130g of toluene, 0.54g of tetrabutylammonium hydrogen sulfate and 54.1g of a 30% aqueous solution of sodium hydroxide, and heated to 60 ℃. 4.1g of allyl bromide was added dropwise thereto, and the mixture was heated and stirred at 60 ℃ for 6 hours. Then, the mixture was allowed to stand, the aqueous layers separated by the two layers were separated, the organic layer was washed with water until the mixture became neutral, and the organic layer was concentrated under reduced pressure (80 ℃ C., 5 mmHg) to remove volatile components, whereby the corresponding alkenyl compound was obtained as a brown solid.
[2 nd stage ]
A200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 25g of the alkenyl compound obtained in the above-mentioned stage 1, 75g of toluene, and 0.06g (5.0X 10 in terms of platinum atom per 1mol of trimethoxysilane, based on the platinum atom) of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in the above-mentioned stage 1 -5 mol) of a reaction solution, 3.7g of trimethoxysilane was charged at an internal temperature of 75 to 85 ℃ and then stirred at 80 ℃ for 1 hour.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 6,100 and a viscosity of 18mm 2 (s) nonvolatile components in an amount of 30% by mass.
Comparative examples 1 to 1]Synthesis of organosilicon Compound 12
A reaction apparatus equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 500g of 2-functional phenylene ether resin (manufactured by Mitsubishi gas chemical Co., ltd., OPE-1000) and 447g of polytetramethoxysilane (manufactured by Moore chemical Co., ltd., M Silicate 51), heated to 90 ℃ and melt-mixed to prepare a uniform solution. 0.22g of dibutyltin dilaurate as a catalyst was added thereto, and subjected to a demethanol reaction at 90 ℃ for 15 hours to obtain the corresponding organosilicon compound.
Comparative examples 1 to 2]Synthesis of organosilicon Compound 13
71.8g of 2-functional phenylene ether resin (manufactured by Mitsubishi gas chemical corporation, OPE-1000) and 45.3g of polymethyltrimethoxysilane (manufactured by Moore chemical corporation, MTMS-A) were charged into se:Sup>A reaction apparatus equipped with se:Sup>A stirrer, se:Sup>A reflux condenser, se:Sup>A dropping funnel and se:Sup>A thermometer, heated to 90 ℃ and melt-mixed to prepare se:Sup>A uniform solution. 0.02g of dibutyltin dilaurate as a catalyst was added thereto, and a demethanol reaction was performed at 90 ℃ for 15 hours, whereby the corresponding organosilicon compound was obtained.
[2] Curable composition and production of cured article thereof
The respective components used in the preparation of the curable composition and the cured article thereof will be described.
[PPE]
Production of PPO (trade Mark) SA90-100 by SABIC Innovative Plastics
[ epoxy resin ]
Epoxy resin 1: DIC (strain) EPICLON HP7200 (dicyclopentadiene type epoxy Compound)
Epoxy resin 2: EPICLON 850S (bisphenol A epoxy resin) manufactured by DIC corporation
[ curing agent ]
2E4MZ (2-ethyl-4-imidazole) manufactured by four kingdoms chemical industries
[ cyanate ester Compound ]
BADCy (2,2-bis (4-cyanate-based phenyl) propane) manufactured by ロンザジャパン
[ organic Metal salt ]
DIC Ltd, cu-NAPHTENATE (copper naphthenate)
[ organosilicon Compound ]
An organosilicon compound: the organosilicon Compounds obtained in examples 1-1 to 1-11 and comparative examples 1-1 and 1-2
[ example 2-1]
PPE, an epoxy resin, a curing agent and the organosilicon compound 1 obtained in example 1-1 were mixed in the mixing ratios (parts by mass, wherein the organosilicon compound is a nonvolatile matter equivalent) shown in tables 1 and 2, and the resulting mixed solution was heated to 60 ℃. After the cyanate ester compound and the organic metal salt were added thereto, the mixture was stirred for 30 minutes to be completely dissolved, thereby obtaining a varnish-like curable composition (resin varnish).
Then, the obtained resin varnish was impregnated into a glass cloth (manufactured by Nissan textile Co., ltd.),
WEA116E, E glass) and then dried by heating at 160 ℃ for 10 minutes to obtain a prepreg. At this time, the content of the resin component was adjusted to be about 55 mass%.
The prepreg sheets thus obtained were stacked in 6 pieces, sandwiched between copper foils (GT-MP manufactured by guhe サーキットフォイル, inc.) and heated and pressed at 200 ℃ for 2 hours under a pressure of 3MPa to obtain an evaluation substrate as a cured product.
Examples 2-2 to 2-11 and comparative examples 2-1 and 2-2
A curable composition and a cured article thereof were produced in the same manner as in example 2-1, except that the organic silicon compound 1 was changed to the organic silicon compounds 2 to 13 obtained in examples 1-2 to 1-11 and comparative examples 1-1 to 1-2, respectively.
Comparative examples 2-3 and 2-4
A curable composition and a cured article thereof were produced in the same manner as in example 2-1, except that the organosilicon compound 1 was changed to gamma-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by shin-Etsu chemical Co., ltd.) as comparative example 2-3 and to phenyltrimethoxysilane (KBM-103, manufactured by shin-Etsu chemical Co., ltd.) as comparative example 2-4.
Comparative examples 2 to 5
A curable composition and a cured article thereof were produced in the same manner as in example 2-1, except that the organosilicon compound 1 was not used.
Each of the evaluation substrates prepared by the above-described procedure was evaluated by the following method.
[ dielectric characteristics ]
The dielectric constant and the dielectric loss tangent of the copper-clad laminate at 2GHz were measured using a cavity resonance "CP461" manufactured by kanto electronic application development (ltd.). The results are shown in tables 1 and 2 below.
[ adhesion Strength of copper foil ]
The peel strength (copper foil adhesion strength) of the copper foil on the surface of the copper-clad laminate was measured by a method in accordance with JIS C6481. At this time, a pattern having a width of 10mm and a length of 100mm was formed on a test piece having a width of 20mm and a length of 100mm, and the copper foil was peeled off at a speed of 50 mm/min using a tensile tester, and the peel strength (kgf/cm) at this time was evaluated as the copper foil adhesion strength. The results are shown in tables 1 and 2 below.
[ TABLE 1]
[ TABLE 2]
As shown in tables 1 and 2, it is understood that the organosilicon compounds obtained in examples 1-1 to 1-11 give cured products having excellent dielectric properties such as adhesion to copper foil, dielectric constant and dielectric loss tangent, as compared with the organosilicon compounds obtained in comparative examples 1-1 and 1-2, gamma-glycidoxypropyltrimethoxysilane and phenyltrimethoxysilane.
Claims (5)
1. An organosilicon compound characterized by being represented by an average structural formula (2):
in the formula, R 1 Independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, R 2 Independent of each otherAn unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms,
A 1 -A 2 represented by the following formula (12) or formula (13):
m is a number from 1 to 3, R 3 Independently represent a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, R 4 Independently of each other, a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, b independently of each other, is a number of 1 to 100, c is a number of 0 or more and less than 2, Z represents a linking group represented by the following formula (3),
in the formula, R 4 Represents the same meaning as above, L represents a linking group selected from the following formulae (4) to (11),
in the formula, R 5 Independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 6 Independently of each other, each represents an alkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 12, and j represents a number of 1 to 1,000.
2. The method for producing an organosilicon compound according to claim 1, wherein a polyphenylene ether compound having a hydroxyl group represented by the average structural formula (15) is reacted with a compound having an isocyanate group and an alkoxysilyl group represented by the formula (16),
in the formula, R 3 、R 4 A, b and Z represent the same meanings as above,
in the formula, R 1 、R 2 、A 2 And m represents the same meaning as described above.
3. A process for producing an organosilicon compound according to claim 1, wherein the method comprises reacting a polyphenylene ether compound having a hydroxyl group represented by the average structural formula (15) with a compound having a functional group reactive with the hydroxyl group and an alkenyl group to obtain an alkenyl compound, and then subjecting the alkenyl compound and a silane compound represented by the formula (17) to hydrosilylation in the presence of a catalyst containing a platinum compound,
in the formula, R 3 、R 4 A, b and Z represent the same meanings as above,
in the formula, R 1 、R 2 And m represents the same meaning as described above.
4. A curable composition comprising the organosilicon compound according to claim 1.
5. A cured article obtained by curing the curable composition according to claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016147410A JP6642325B2 (en) | 2016-07-27 | 2016-07-27 | Resin modifier for high frequency substrate materials composed of organosilicon compounds |
| JP2016-147410 | 2016-07-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107663273A CN107663273A (en) | 2018-02-06 |
| CN107663273B true CN107663273B (en) | 2022-12-30 |
Family
ID=61075793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710614721.5A Active CN107663273B (en) | 2016-07-27 | 2017-07-26 | Organosilicon compound, method for producing same, and curable composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6642325B2 (en) |
| KR (1) | KR102356533B1 (en) |
| CN (1) | CN107663273B (en) |
| TW (1) | TWI660977B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW202012481A (en) * | 2018-07-20 | 2020-04-01 | 日商三菱瓦斯化學股份有限公司 | Resin composition, prepreg, metal foil-clad laminated plate, resin sheet, and printed-wiring board |
| CN109265963A (en) * | 2018-09-11 | 2019-01-25 | 广东国立科技股份有限公司 | A kind of high-impact high temperature resistant halogen-free flame-retardant PPO alloy material and preparation method thereof |
| JP2021031612A (en) | 2019-08-27 | 2021-03-01 | 信越化学工業株式会社 | Polyphenylene ether resin composition and mixture |
| JP7276245B2 (en) * | 2020-05-15 | 2023-05-18 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane compositions and articles |
| CN117836341A (en) | 2021-08-25 | 2024-04-05 | 三菱瓦斯化学株式会社 | Resin composition, cured product, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093600A (en) * | 1976-04-30 | 1978-06-06 | Union Carbide Corporation | Silane end-capped polyarylene polyethers |
| EP0457351A2 (en) * | 1990-05-17 | 1991-11-21 | Mitsubishi Petrochemical Co., Ltd. | Process for producing silane-modified polyphenylene ether and thermoplastic resin composition containing the same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02124936A (en) * | 1988-11-04 | 1990-05-14 | Japan Synthetic Rubber Co Ltd | Silylated polyether |
| US5143988A (en) * | 1989-11-27 | 1992-09-01 | Virginia Tech Intellectual Properties, Inc. | High refractive-index hybrid material prepared by titanium alkoxide and a phosphine containing oligomer |
| JPH0423831A (en) * | 1990-05-17 | 1992-01-28 | Mitsubishi Petrochem Co Ltd | Method for producing terminal group-modified polyphenylene ether |
| JPH0433923A (en) * | 1990-05-30 | 1992-02-05 | Mitsubishi Petrochem Co Ltd | Production of alkoxysilylated polyphenylene ether |
| JPH06200015A (en) * | 1992-12-28 | 1994-07-19 | Nippon G Ii Plast Kk | Production of alkoxysilylated polyphenylene ether |
| JP2000221720A (en) * | 1999-01-28 | 2000-08-11 | Canon Inc | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus |
| DE10355318A1 (en) * | 2003-11-27 | 2005-06-23 | Wacker-Chemie Gmbh | Process for the preparation of organyloxysilyl-terminated polymers |
| JP4189756B2 (en) | 2004-05-18 | 2008-12-03 | 荒川化学工業株式会社 | Process for producing alkoxysilyl group-containing silane-modified phenylene ether resin, alkoxysilyl group-containing silane-modified phenylene ether resin, alkoxysilyl group-containing silane-modified phenylene ether resin composition, and phenylene ether resin-silica hybrid cured product |
| JP5971934B2 (en) * | 2011-12-08 | 2016-08-17 | 古河電気工業株式会社 | Copper-clad laminate for high-frequency substrate and surface-treated copper foil used therefor |
-
2016
- 2016-07-27 JP JP2016147410A patent/JP6642325B2/en active Active
-
2017
- 2017-07-24 TW TW106124718A patent/TWI660977B/en active
- 2017-07-24 KR KR1020170093246A patent/KR102356533B1/en active Active
- 2017-07-26 CN CN201710614721.5A patent/CN107663273B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093600A (en) * | 1976-04-30 | 1978-06-06 | Union Carbide Corporation | Silane end-capped polyarylene polyethers |
| EP0457351A2 (en) * | 1990-05-17 | 1991-11-21 | Mitsubishi Petrochemical Co., Ltd. | Process for producing silane-modified polyphenylene ether and thermoplastic resin composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107663273A (en) | 2018-02-06 |
| KR102356533B1 (en) | 2022-01-27 |
| JP6642325B2 (en) | 2020-02-05 |
| TW201817769A (en) | 2018-05-16 |
| TWI660977B (en) | 2019-06-01 |
| JP2018016709A (en) | 2018-02-01 |
| KR20180012701A (en) | 2018-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107663273B (en) | Organosilicon compound, method for producing same, and curable composition | |
| US5945555A (en) | Silatrane derivative, method for manufacturing same, adhesion promoter, and curable silicone composition | |
| CN109694474B (en) | Organosilicon compound, method for producing same, and curable composition | |
| TWI787910B (en) | Aminated imide compound, aminated imide composition, curing agent, epoxy resin composition, production method of aminated imide compound, sealing material, and adhesive | |
| EP3594220B1 (en) | Organosilicon compound and method for producing same | |
| EP3594261B1 (en) | Polyoxyalkylene group-containing organosilicon compound and method for producing same | |
| JP2017043560A (en) | Nitrogen-containing organic silicon compound and resin composition | |
| CN111607091A (en) | Organosilicon compound, method for producing same, and curable composition | |
| KR20180037989A (en) | Sulfur containing organosilicon compound and resin composition | |
| US7053233B2 (en) | Silane compound having at least two protected functional groups and method for preparing the same | |
| CN112442267A (en) | Polyphenylene ether resin composition and mixture | |
| JPH0364532B2 (en) | ||
| US10683312B2 (en) | Glycoluril ring-containing organosilicon compound and making method | |
| CN104650131B (en) | Silane compound, method for preparing the same, and polycarbonate resin composition comprising the same | |
| TWI654217B (en) | Organic silicon compound and its manufacturing method | |
| KR20230013062A (en) | Organopolysiloxanes and compositions containing them | |
| TW202132404A (en) | Curable composition | |
| JPH10139854A (en) | Epoxy resin, epoxy resin composition and cured product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |