CN116693781A - Block copolymer, resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit board - Google Patents

Block copolymer, resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit board Download PDF

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Publication number
CN116693781A
CN116693781A CN202310135115.0A CN202310135115A CN116693781A CN 116693781 A CN116693781 A CN 116693781A CN 202310135115 A CN202310135115 A CN 202310135115A CN 116693781 A CN116693781 A CN 116693781A
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Prior art keywords
block copolymer
component
resin
mass
resin composition
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CN202310135115.0A
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Chinese (zh)
Inventor
松冈裕太
服部刚树
助川敬
近藤知宏
荒木祥文
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Asahi Kasei Corp
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Asahi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
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Abstract

The present invention relates to a block copolymer, a resin composition, a cured product, a resin film, a prepreg, a laminate, and a material for an electronic circuit board, and aims to provide a block copolymer which can give a cured product having a low dielectric constant, a low dielectric loss tangent, and excellent strength characteristics. A block copolymer having: a polymer block (A) mainly composed of vinyl aromatic monomer units; and a polymer block (B) mainly composed of conjugated diene monomer units and/or a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units, which satisfies the following conditions (i) to (ii). < condition (i) > the weight average molecular weight of the block copolymer is 3.5 ten thousand or less. < condition (ii) > the content of the vinyl aromatic monomer unit in the block copolymer is 55 mass% or more and 95 mass% or less.

Description

Block copolymer, resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit board
Technical Field
The present invention relates to a block copolymer, a resin composition, a cured product, a resin film, a prepreg, a laminate, and a material for an electronic circuit board.
Background
In recent years, with remarkable progress in information network technology and expansion of services using an information network, electronic devices are demanded to have a large capacity of information and a high processing speed.
In order to meet these demands, materials with low dielectric loss are demanded for various substrate materials such as printed boards and flexible substrates.
Conventionally, in order to obtain a material having a small dielectric loss, various materials such as a resin cured product mainly composed of a thermosetting resin such as an epoxy resin or a thermoplastic resin such as a polyphenylene ether resin having a low dielectric constant and/or a low dielectric loss tangent and excellent mechanical properties such as strength have been studied and disclosed.
However, the materials disclosed in the prior art have room for improvement from the viewpoints of low dielectric constant and low dielectric loss tangent, and there is a problem that the amount of information and the processing speed are limited when they are used for printed boards.
In order to solve this problem, various rubber components have been conventionally proposed as modifiers for the thermosetting resin or thermoplastic resin.
For example, patent document 1 discloses, as a modifier for low dielectric loss tangent and low dielectric constant of a polyphenylene ether resin, at least one elastomer selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin-based compound, a hydride thereof, and a homopolymer of a vinyl aromatic compound.
Patent document 2 discloses a styrene elastomer as a modifier for use in low dielectric loss tangent and low dielectric constant of an epoxy resin.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2021-147486
Patent document 2: japanese patent laid-open No. 2020-15861
Disclosure of Invention
Problems to be solved by the invention
However, the resin compositions using the modifiers disclosed in patent documents 1 and 2 are insufficient in terms of low dielectric constant and low dielectric loss tangent, and have a problem that the strength is lowered by the addition of the modifiers, and sufficient strength cannot be obtained.
Accordingly, an object of the present invention is to provide a block copolymer which can give a cured product having a low dielectric constant, a low dielectric loss tangent and excellent strength characteristics, and a resin composition containing the block copolymer.
Means for solving the problems
The present inventors have conducted intensive studies to solve the problems of the prior art described above, and as a result, have found that a cured product of a resin composition containing a block copolymer having a predetermined structure has a low dielectric constant and a low dielectric loss tangent and is excellent in strength characteristics, and have completed the present invention.
Namely, the present invention is as follows.
[1]
A block copolymer having:
a polymer block (A) mainly composed of vinyl aromatic monomer units; and
a polymer block (B) mainly composed of conjugated diene monomer units and/or a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units,
the block copolymer satisfies the following conditions (i) to (ii).
< condition (i) >
The weight average molecular weight of the block copolymer is 3.5 ten thousand or less.
< condition (ii) >
The content of the vinyl aromatic monomer unit in the block copolymer is 55 to 95 mass%.
[2]
The block copolymer according to the above [1], which further satisfies the following condition (iii).
< condition (iii) >
The polymer block (B) and/or the polymer block (C) contains a unit (a) derived from 1, 2-bonding and/or 3, 4-bonding and a unit (B) derived from 1, 4-bonding, and the content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding is 80% or less, assuming that the total content of the polymer block (B) and/or the polymer block (C) is 100%.
[3]
A resin composition comprising:
component (I): the block copolymer of [1] or [2] above; and
At least one component selected from the group consisting of the following components (II) to (IV).
Component (II): free radical initiator
Component (III): polar resin (excluding component (I))
Component (IV): curing agent (excluding component (II))
[4]
The resin composition according to the above [3], wherein the component (III) is at least one selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, liquid crystal polyester resins and fluorine resins.
[5]
A cured product comprising the block copolymer according to [1] or [2 ].
[6]
A cured product of the resin composition according to [3] or [4 ].
[7]
A resin film comprising the resin composition according to [3] or [4 ].
[8]
A prepreg which is a composite of a substrate and the resin composition according to the above [3] or [4 ].
[9]
The prepreg according to [8], wherein the substrate is glass cloth.
[10]
A laminate comprising the resin film according to [7] above and a metal foil.
[11]
A laminate comprising a cured product of the prepreg according to [8] or [9] and a metal foil.
[12]
A material for an electronic circuit board, which comprises the cured product of [6 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a block copolymer and a resin composition containing the block copolymer can be provided, wherein the block copolymer can obtain a cured product having a low dielectric constant, a low dielectric loss tangent and excellent strength characteristics.
Detailed Description
Hereinafter, a specific embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail.
The following embodiments are examples for illustrating the present invention, and are not intended to limit the present invention to the following, but the present invention can be implemented by various modifications within the scope of the gist thereof.
[ Block copolymer ]
The block copolymer of the present embodiment comprises: a polymer block (A) mainly composed of vinyl aromatic monomer units (hereinafter sometimes referred to as a polymer block (A)); and a polymer block (B) mainly composed of conjugated diene monomer units (hereinafter sometimes referred to as polymer block (B)) and/or a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units (hereinafter sometimes referred to as polymer block (C)).
The block copolymer of the present embodiment satisfies the following conditions (i) to (ii).
< condition (i) >
The weight average molecular weight of the block copolymer is 3.5 ten thousand or less.
< condition (ii) >
The content of the vinyl aromatic monomer unit in the block copolymer is 55 to 95 mass%.
According to the block copolymer of the present embodiment, a cured product of a resin composition having a low dielectric constant, a low dielectric loss tangent, and excellent strength characteristics can be obtained.
The conjugated diene monomer unit refers to a structural unit derived from a conjugated diene compound in a polymer block or a block copolymer produced by polymerization of the conjugated diene compound.
The conjugated diene compound is a diene having a pair of conjugated double bonds.
Examples of the conjugated diene compound include, but are not limited to, 1, 3-butadiene, 2-methyl-1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, 1, 3-hexadiene, and 1, 3-cyclohexadiene.
Among these, 1, 3-butadiene and isoprene are preferable, and 1, 3-butadiene is more preferable. The 1, 3-butadiene and isoprene are widely and easily available, and are advantageous from the viewpoint of cost, and are easily copolymerized with styrene which is widely used as a vinyl aromatic compound to be described later.
These compounds may be used singly or in combination of two or more.
The conjugated diene compound may be a compound of biological origin.
The vinyl aromatic monomer unit means a structural unit derived from a vinyl aromatic compound in a polymer block or a block copolymer obtained by polymerizing a vinyl aromatic compound.
Examples of the vinyl aromatic compound include, but are not limited to, styrene, α -methylstyrene, p-methylstyrene, divinylbenzene, 1-diphenylethylene, N-dimethyl-p-aminoethylstyrene, N-diethyl-p-aminoethylstyrene, and the like.
These compounds may be used singly or in combination of two or more.
The block copolymer of the present embodiment comprises: a polymer block (A) mainly composed of vinyl aromatic monomer units; and a polymer block (B) mainly composed of conjugated diene monomer units and/or a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units.
Namely, the polymer block (A) and the polymer block (B), the polymer block (A) and the polymer block (C), or the polymer block (A), the polymer block (B) and the polymer block (C).
The polymer block (A) is composed mainly of vinyl aromatic monomer units. The term "mainly" means that the vinyl aromatic monomer unit is substantially composed of vinyl aromatic monomer units, and means that no other monomer is intentionally added.
The polymer block (B) is composed mainly of conjugated diene monomer units. The term "mainly" means that the conjugated diene monomer unit is substantially composed of conjugated diene monomer units, and means that no other monomer than conjugated diene monomer units is intentionally added.
The content of the polymer block (a) in the block copolymer of the present embodiment can be measured as follows: the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation was measured by a method using a nuclear magnetic resonance apparatus (NMR) (a method described in y.tanaka, et al, RUBBER CHEMISTRY and TECHNOLOGY, 685 (1981), hereinafter referred to as "NMR method").
The content of the polymer block (a) in the block copolymer of the present embodiment is preferably 15 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 25 to 85% by mass, from the viewpoint of improvement in strength of a cured product due to intertwining of the polymer block (a) composed of vinyl aromatic monomer units, which will be described later.
When the block copolymer of the present embodiment contains the polymer block (B), the content of the polymer block (B) can be measured by NMR.
The content of the polymer block (B) in the block copolymer of the present embodiment is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass, from the viewpoints of reactivity and compatibility of the polymer blocks (B) each composed of conjugated diene monomer units and/or the above block copolymer with the component (II), component (III) and component (IV) described later.
The polymer block (C) is composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit, and does not contain a monomer other than the vinyl aromatic monomer unit and the conjugated diene monomer unit.
The polymer block (C) has a structure in which a vinyl aromatic monomer unit and a conjugated diene monomer unit are intentionally used as structural units, and can be distinguished from the polymer block (a) and the polymer block (B) described above.
The vinyl aromatic compound and the conjugated diene compound used for forming the vinyl aromatic monomer unit and the conjugated diene monomer unit contained in the polymer block (C) may be any compound that can be used for the polymer block (a) and the polymer block (B).
The distribution state of the vinyl aromatic monomer units in the polymer block (C) is not particularly limited, and the vinyl aromatic monomer units may be uniformly distributed in the random copolymer block or may be distributed stepwise. In addition, the vinyl aromatic monomer unit may be uniformly distributed and/or the vinyl aromatic monomer unit may be distributed stepwise, or a plurality of segments having different vinyl aromatic monomer unit contents may be present.
When the block copolymer of the present embodiment contains the polymer block (C), the content of the polymer block (C) can be measured by NMR.
The content of the polymer block (C) in the block copolymer of the present embodiment is preferably 20 to 90% by mass, more preferably 35 to 85% by mass, still more preferably 30 to 80% by mass, still more preferably 35 to 75% by mass, and still more preferably 40 to 70% by mass, from the viewpoints of reactivity and compatibility of conjugated diene monomer units in the polymer block (C) with each other and/or the above block copolymer with the component (II), component (III) and component (IV) described later.
The block copolymer of the present embodiment may have a copolymer block (D) obtained by copolymerizing a compound other than the above-mentioned polymer blocks (a) to (C) with a conjugated diene compound and/or a vinyl aromatic compound in a range not impairing the dielectric properties of the desired cured product, that is, in a range not impairing the low dielectric loss tangent and low dielectric constant.
For example, in the case of producing the block copolymer of the present embodiment containing the copolymer block (D) by anionic polymerization, methyl Methacrylate (MMA) can be copolymerized with a vinyl aromatic compound and a conjugated diene compound, but if MMA is contained, the dielectric properties of the block copolymer of the present embodiment tend to be lowered, that is, the dielectric constant and/or dielectric loss tangent tend to be improved.
The structure of the block copolymer of the present embodiment is not particularly limited, and examples thereof include block copolymers having a structure represented by the following formula.
(a-b) n 、b-(a-b) n 、a-(b-a) n 、(a-b) m -X、(b-a) m -X、[(a-b) n ] m -X、[(b-a) n ] m -X、[b-(a-b) n ] m -X、[a-(b-a) n ] m -X、[(a-b) n -a] m -X、[(b-a) n -b] m -X、
(a-c) n 、c-(a-c) n 、a-(c-a) n 、(a-c) m -X、(c-a) m -X、[(a-c) n ] m -X、[(c-a) n ] m -X、[c-(a-c) n ] m -X、[a-(c-a) n ] m -X、[(a-c) n -a] m -X、[(c-a) n -c] m -X、
c-(b-a) n 、c-(a-b) n 、
c-(a-b-a) n 、c-(b-a-b) n 、
a-c-(b-a) n 、a-c-(a-b) n 、
a-c-(b-a) n -b、[(a-b-c) n ] m -X、
[a-(b-c) n ] m -X、[(a-b) n -c] m -X、
[(a-b-a) n -c] m -X、
[(b-a-b) n -c] m -X、[(c-b-a) n ] m -X、
[c-(b-a) n ] m -X、[c-(a-b-a) n ] m -X、[c-(b-a-b) n ] m -X
a-(b-c) n 、a-(c-b) n 、
a-(c-b-c) n 、a-(b-c-b) n 、
c-a-(b-c) n 、c-a-(c-b) n 、
c-a-(b-c) n -b、[(c-b-a) n ] m -X、
[c-(b-a) n ] m -X、[(c-b) n -a] m -X、
[(c-b-c) n -a] m -X、
[(b-c-b) n -a] m -X、[(a-b-c) n ] m -X、
[a-(b-c) n ] m -X、[a-(c-b-c) n ] m -X、[a-(b-c-b) n ] m -X
b-(a-c) n 、b-(c-a) n 、
b-(c-a-c) n 、b-(a-c-a) n 、
c-b-(a-c) n 、c-b-(c-a) n 、
c-b-(a-c) n -a、[(c-a-b) n ] m -X、
[c-(a-b) n ] m -X、[(c-a) n -b] m -X、
[(c-a-c) n -b] m -X、
[(b-a-c) n ] m -X、
[b-(a-c) n ] m -X、[b-(c-a-c) n ] m -X、[b-(a-c-a) n ] m -X
In the general formulae, a represents the polymer block (a), B represents the polymer block (B), and C represents the polymer block (C).
n is an integer of 1 or more, preferably an integer of 1 to 5.
m is an integer of 2 or more, preferably an integer of 2 to 11.
X represents the residue of a coupling agent or the residue of a multifunctional initiator.
The polymer block (a) is a polymer block mainly composed of vinyl aromatic monomer units and is thus amorphous. In the resin composition and the cured product of the present embodiment described later, the polymer block (a) is contained, whereby the intertwining strength and heat resistance are improved.
The polymer block (B) is a polymer block mainly composed of conjugated diene monomer units and thus has radical reactivity.
In the resin composition and the cured product of the present embodiment described later, the heat resistance tends to be improved by the reaction of the respective polymer blocks and/or the block copolymer of the present embodiment.
When the block copolymer of the present embodiment is formed into a resin composition with the component (III) and/or the component (IV) which are not free-radical reactive, the conjugated diene monomer unit has smaller steric hindrance than the vinyl aromatic monomer unit, and therefore is compatible with the component (III) and/or the component (IV), and the resin composition and the cured product of the present embodiment tend to have excellent strength and heat resistance.
In addition, by improving the reactivity and compatibility of the respective polymer blocks and/or block copolymers, the resin composition and the cured product of the present embodiment, which will be described later, can suppress the decrease in the mobility and polarization of the polymer due to an external electric field, and the resin composition and the cured product can have a low dielectric loss tangent and a low dielectric constant.
Since the polymer block (C) is a polymer block containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, the strength-improving effect by the entanglement with the polymer block (a) mainly containing a vinyl aromatic monomer unit, and the radical reactivity and compatibility-improving effect with other components than the polymer blocks (a) and (B) can be expected. On the other hand, the strength improvement effect by the intertwining of the polymer blocks (a) tends to be inferior to that by the intertwining of the polymer blocks (a).
As described later, the resin composition of the present embodiment contains the block copolymer of the present embodiment (component (I)) and component (II): radical initiator, component (III): polar resin, component (IV): and (3) a curing agent.
Component (II), component (III) and component (IV) have polar groups.
The vinyl aromatic compound is more excellent in compatibility with the component (II), the component (III) and the component (IV) than the conjugated diene compound in terms of solubility parameter, but the block copolymer of the present embodiment is reduced in steric hindrance at the time of copolymerization of the conjugated diene compound, and the compatibility with the component (III) and the component (IV) is improved if the block copolymer has the polymer block (C).
In the present embodiment, in order to obtain a resin composition and a cured product having high strength, low dielectric loss tangent and low dielectric constant, the block copolymer of the present embodiment has a polymer block (a) mainly composed of a vinyl aromatic monomer unit in terms of intertwining of a polymer composed of a vinyl aromatic compound, and has a polymer block (B) and/or a polymer block (C) in terms of the reactivity and/or compatibility.
In addition, as component (III) constituting the resin composition of the present embodiment: when a resin containing an aromatic ring such as a polyphenylene ether resin is used as the polar resin, the block copolymer of the present embodiment tends to have improved compatibility and further improved strength of a cured product by containing the polymer block (a) mainly composed of a vinyl aromatic monomer unit.
The block copolymer contained in the resin composition of the present embodiment satisfies the conditions (i) and (ii).
< condition (i) >
The weight average molecular weight of the block copolymer of the present embodiment is 3.5 ten thousand or less.
The weight average molecular weight was determined by measuring the molecular weight of the peak of a chromatogram obtained by measurement by Gel Permeation Chromatography (GPC) based on a calibration curve (prepared by using the peak molecular weight of a standard polystyrene) obtained by measurement of a commercially available standard polystyrene. Specifically, the measurement can be performed by the method described in examples described below.
The molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
The molecular weight distribution of a single peak of the block copolymer according to the present embodiment as measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, and further preferably 2.5 or less.
The block copolymer of the present embodiment has a weight average molecular weight of 3.5 ten thousand or less, and is mixed with the component (III) constituting the resin composition of the present embodiment, which will be described later: polar resin, component (IV): the compatibility of the curing agent is improved, the strength of the resin composition and the cured product can be improved, and the dielectric loss tangent and the dielectric constant can be reduced.
In the case of producing a prepreg using the resin composition of the present embodiment, when a substrate such as a glass cloth described later is impregnated with a varnish described later, the weight average molecular weight of the block copolymer of the present embodiment is 3.5 ten thousand or less, so that the permeability to the substrate is improved, and a uniform prepreg tends to be produced.
From the above-described points, the weight average molecular weight of the block copolymer of the present embodiment is preferably 3.0 ten thousand or less, more preferably 2.5 ten thousand or less, still more preferably 2.0 ten thousand or less, still more preferably 1.5 ten thousand or less, still more preferably 1.0 ten thousand or less. The lower limit is not particularly limited, but is preferably 500 or more in view of the suppression of tackiness and good handleability of the block copolymer of the present embodiment.
The weight average molecular weight and molecular weight distribution of the block copolymer of the present embodiment can be controlled to the above numerical ranges by adjusting the polymerization conditions such as the amount of monomer added, the timing of addition, the polymerization temperature, and the polymerization time.
< condition (ii) >
The content of the vinyl aromatic monomer unit in the block copolymer of the present embodiment is 55 mass% or more and 95 mass% or less.
The above numerical ranges tend to have excellent compatibility with the component (II), the component (III) and the component (IV) described below in terms of solubility parameters.
By setting the content of the vinyl aromatic monomer unit in the block copolymer of the present embodiment to 55 mass% or more, compatibility with the component (II), the component (III) and the component (IV) described later is improved, and strength of the resin composition and the cured product of the present embodiment can be improved, and low dielectric loss tangent and low dielectric constant can be achieved.
The content of the vinyl aromatic monomer unit in the block copolymer of the present embodiment is preferably 57 mass% or more, more preferably 60 mass% or more, still more preferably 63 mass% or more, still more preferably 65 mass% or more, and particularly preferably 67 mass% or more, from the viewpoint of solubility parameters.
By setting the content of the vinyl aromatic monomer unit to 95 mass% or less, the reactivity with the component (II), the component (III), and the component (IV) described later, and the reactivity with each other of the block copolymer of the present embodiment can be ensured. Preferably 90 mass% or less, more preferably 85 mass% or less.
According to the findings of the present inventors, the dielectric properties of the block copolymer and the state of the cured product are correlated to some extent, and by curing the block copolymer of the present embodiment in a state where it reacts or is compatible with other components, the molecular chains are less likely to move, and the dielectric properties of the cured product are improved, that is, the dielectric constant tends to be low. Therefore, from the viewpoint of improving the dielectric properties of the cured product, it is preferable to control the dielectric constant or the dielectric properties of the block copolymer of the present embodiment, as well as the reactivity and compatibility with other components.
When the content of the vinyl aromatic monomer unit in the block copolymer of the present embodiment is 55 mass% or more, compatibility with the component (II), the component (III) and the component (IV) described later becomes good, and the entanglement due to the aggregation of the polymer block (a) mainly composed of the vinyl aromatic monomer unit increases, so that high strength can be achieved, and low dielectric loss tangent and low dielectric constant can be achieved.
The content of the vinyl aromatic monomer unit in the block copolymer (I) can be controlled to the above numerical range by adjusting the polymerization conditions such as the amount of the monomer to be added, the timing of addition, and the polymerization temperature, and specifically, can be calculated by the method described in examples to be described later.
The block copolymer of the present embodiment preferably also satisfies the condition (iii).
< condition (iii) >
The polymer block (B) and/or the polymer block (C) contains a unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (hereinafter sometimes referred to as a unit (a)) and a unit (B) derived from 1, 4-bonding (hereinafter sometimes referred to as a unit (B)), and the content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding is 80% or less, assuming that the total content of the conjugated diene monomer units in the polymer block (B) and/or the polymer block (C) is 100%.
In the calculation of the content of the unit (a) in the block copolymer, the total content of the conjugated diene monomer units in the polymer block (B) and the polymer block (C) is 100% when the block copolymer contains both the polymer block (B) and the polymer block (C), the content of the polymer block (B) is 100% when the block copolymer contains only the polymer block (B), and the content of the conjugated diene monomer units in the polymer block (C) is 100% when the block copolymer contains only the polymer block (C).
In the case where both of 1, 2-bond and 3, 4-bond are contained, the total content of 1, 2-bond and 3, 4-bond is the content of the unit (a) (vinyl bond amount).
The unit (a) has higher radical reactivity than the unit (b). When the resin composition of the present embodiment or the resin varnish containing the block copolymer of the present embodiment, which will be described later, is stored before curing, the content of the unit (a) is set to 80% or less, whereby the resin composition and the resin varnish tend to exhibit sufficient storage stability.
The lower limit of the content of the unit (a) is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more, and still more preferably 50% or more, from the viewpoints of the reactivity of conjugated diene monomer units in the block copolymer of the present embodiment and the reactivity of the block copolymer with other components.
The content of the unit (a) can be controlled to the above numerical range by using a regulator such as a polar compound at the time of polymerization, and can be calculated by the method described in examples described later.
Examples of the regulator include tertiary amine compounds and ether compounds. Preferably, tertiary amine compounds are used.
The tertiary amine compound is a compound of the general formula R1R2R3N (wherein R1, R2 and R3 are hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbon groups having a tertiary amino group).
Examples of the tertiary amine compound include, but are not limited to, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -tetraethylethylenediamine, 1, 2-dipiperidylethane, trimethylaminoethylpiperazine, N, N, N ', N ' -pentamethylethylenetriamine, N, N ' -dioctyl-p-phenylenediamine, and the like.
The block copolymer of the present embodiment may be a hydrogenated block copolymer in which an aliphatic double bond of a conjugated diene compound is hydrogenated within a range that does not impair the curing reaction.
The method for hydrogenating the block copolymer is not particularly limited, and conventionally known methods can be applied.
In the hydrogenation reaction, a hydrogenation catalyst may be used.
As the hydrogenation catalyst, for example, use is made of: (1) A supported heterogeneous hydrogenation catalyst comprising a metal such as Ni, pt, pd, ru supported on carbon, silica, alumina, diatomaceous earth or the like; (2) A so-called Ziegler-type hydrogenation catalyst using a reducing agent such as an organic acid salt such as Ni, co, fe, cr or a transition metal salt such as acetylacetonate and an organic aluminum; (3) A homogeneous hydrogenation catalyst such as a so-called organometallic complex, for example, an organometallic compound such as Ti, ru, rh, zr.
As the hydrogenation catalyst, specifically, those described in Japanese patent publication No. 42-8704, japanese patent publication No. 43-6636, japanese patent publication No. 63-4841, japanese patent publication No. 1-37970, japanese patent publication No. 1-53851 and Japanese patent publication No. 2-9041 can be used.
Preferred hydrogenation catalysts include cyclopentadienyl titanium compounds and/or reducing organometallic compounds.
As the cyclopentadienyl titanium compound, a compound described in JP-A-8-109219 can be used. Examples of the cyclopentadienyl titanium compound include compounds having at least 1 ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton, such as dicyclopentadiene titanium dichloride and mono (penta-methylcyclopentadienyl) titanium trichloride. The cyclopentadienyl titanium compound may contain 1 kind of the above skeleton alone or in combination of 2 kinds.
Examples of the reducing organometallic compound include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds. The number of these may be 1 alone or 2 or more.
The hydrogenation rate of the block copolymer can be controlled by appropriately adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount, and the like in the hydrogenation method. The hydrogenation reaction is preferably carried out at a temperature of 55 to 200 ℃, more preferably 60 to 170 ℃, still more preferably 65 to 160 ℃. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15MPa, more preferably 0.2 to 10MPa, and still more preferably 0.3 to 5MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.
The hydrogenation reaction may employ any of a batch process, a continuous process, or a combination thereof.
When the curing reaction in the case of obtaining a cured product of the present embodiment to be described later is a radical reaction, the hydrogenation rate of the block copolymer of the present embodiment is preferably 5 to 95%, more preferably 10 to 90%, and even more preferably 13 to 87% from the viewpoint of the balance between the curing reactivity and the thermal stability. In the case where the curing reaction is other than the radical reaction, the hydrogenation rate may be arbitrarily selected from 0 to 100% in terms of compatibility with other components of the block copolymer of the present embodiment.
[ method for producing Block copolymer ]
The block copolymer of the present embodiment can be produced, for example, by living anionic polymerization in a hydrocarbon solvent using a polymerization initiator such as an organic alkali metal compound.
Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; etc.
Examples of the polymerization initiator include organic alkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds and organic amino alkali metal compounds which are generally known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds.
Examples of the alkali metal include lithium, sodium, and potassium.
Examples of the organic alkali metal compound include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, including compounds containing 1 lithium in 1 molecule, dilithium compounds containing a plurality of lithium in 1 molecule, trilithium compounds, and tetralithium compounds.
Specific examples of the organic alkali metal compound include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, a reaction product of diisopropenylbenzene and sec-butyllithium, and a reaction product of divinylbenzene and sec-butyllithium and a small amount of 1, 3-butadiene. Further, lithium compounds having 1- (t-butoxy) propyl lithium disclosed in U.S. Pat. No. 5,708,092 and 1 to several molecules of isoprene monomer inserted for improving the solubility thereof, lithium alkyls having a siloxane group such as 1- (t-butyldimethylsiloxy) hexyl lithium disclosed in U.S. Pat. No. 2,241,239, and lithium amides such as lithium alkyls having an amino group, lithium diisopropylamine and lithium hexamethyldisilazide disclosed in U.S. Pat. No. 5,527,753 can be used.
As a method for polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be applied.
The polymerization method may be, for example, any of batch polymerization, continuous polymerization, or a combination thereof. In order to obtain a homogeneous polymer block, batch polymerization is preferred.
The polymerization temperature is preferably from 0℃to 180℃and more preferably from 30℃to 150 ℃. The polymerization time varies depending on the conditions, and is usually within 48 hours, preferably 0.1 to 10 hours. The atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen. The polymerization pressure is not particularly limited as long as it is set in a pressure range in which the monomer and the solvent can be maintained in a liquid phase in the above temperature range. In addition, care must be taken not to mix impurities into the polymerization system, such as water, oxygen, carbon dioxide, etc., which deactivate the catalyst and living polymer.
Further, at the end of the polymerization step, a coupling reaction may be performed by adding a desired amount of a coupling agent having a 2-function or more, and the coupling ratio is preferably 40% or less, more preferably 30% or less, still more preferably 20% or less, and even more preferably no coupling agent is contained.
The 2-functional coupling agent may be any conventionally known coupling agent, and is not particularly limited.
Examples of the 2-functional coupling agent include, but are not limited to, alkoxy silane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dihalides such as dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalate esters.
The 3-functional or higher polyfunctional coupling agent may be any conventionally known coupling agent, and is not particularly limited.
Examples of the 3-or higher-functional coupling agent include, but are not limited to, 3-or higher-polyol; multi-epoxy compounds such as epoxidized soybean oil, diglycidyl bisphenol a, and 1, 3-bis (N-N' -diglycidyl aminomethyl) cyclohexane; general formula R 4 -nSiX n (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), for example, methyltrichlorosilane, t-butyltrichlorosilane, silicon tetrachloride, bromide thereof, and the like; general formula R 4 -nSnX n (herein, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), for example, a polyvalent halide such as methyltin trichloride, t-butyltin trichloride, or tin tetrachloride. In addition, dimethyl carbonate, diethyl carbonate, and the like may also be used.
The block copolymer solution of the present embodiment obtained as described above may be subjected to removal of catalyst residues as needed, and the block copolymer may be separated from the solution.
In the case of producing a block copolymer by anionic living polymerization, a polymerization initiator and a compound containing a metal atom in a hydrogenation catalyst in the hydrogenation reaction react with moisture in the air or the like in a desolvation step or the like to produce a specific metal compound, and the specific metal compound tends to remain in the block copolymer. When these compounds are contained in the cured product, the dielectric constant and dielectric loss tangent tend to increase, and further ion migration tends to occur easily in electronic material applications.
Examples of the metal compound to be remained include compounds of metals contained in the polymerization initiator and hydrogenation catalyst, for example, oxides containing respective atoms such as titanium oxide, amorphous titanium oxide, orthotitanic acid or metatitanic acid, titanium hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, cobalt hydroxide, and the like, composite oxides of respective atoms such as lithium titanate, barium titanate, strontium titanate, nickel iron oxide, and the like, and dissimilar metals.
In the cured product of the resin composition of the present embodiment, the residual amount of the metal compound in the block copolymer is preferably 150ppm or less, more preferably 130ppm or less, still more preferably 100ppm or less, and still more preferably 90ppm or less in terms of the amount of the residual metal, from the viewpoints of achieving low dielectric constant and low dielectric loss tangent, and making it difficult for ion migration to occur. Specific examples of the residual metal include Ti, ni, li, co.
As a method for reducing the amount of residual metal in the block copolymer of the present embodiment, a conventionally known method can be applied, and is not particularly limited. For example, use is made of: a method of adding water and carbon dioxide after the hydrogenation reaction of the block copolymer to neutralize the hydrogenation catalyst residue; a method of neutralizing hydrogenation catalyst residues by adding an acid in addition to water and carbon dioxide. Specifically, the method described in Japanese patent application No. 2014-557427 can be applied. Even if these metal removal methods are used, water containing a hydroxide of a metal compound is mixed in the step of desolvation of the block copolymer, and therefore, the residual metal generally contains about 1 to 15 ppm. Thus, the amount of metal added to the block copolymer is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more, still more preferably 50% or more, still more preferably 60% or more.
The amount of the residual metal in the block copolymer can be reduced by reducing the amounts of the polymerization initiator and the hydrogenation catalyst added, but if the amount of the polymerization initiator is reduced, the molecular weight of the block copolymer is increased, and if the amount falls outside the preferable molecular weight range, the strength of the cured product tends to be reduced. In addition, when the amount of the hydrogenation catalyst is reduced during the hydrogenation reaction, the hydrogenation reaction time is prolonged and the hydrogenation reaction temperature is increased, so that productivity tends to be significantly lowered.
Examples of the solvent separation method for removing the block copolymer from the solution of the block copolymer include: adding a polar solvent such as acetone or alcohol, which is a poor solvent for the block copolymer, to the hydrogenated reaction solution to precipitate and recover the block copolymer; a method in which the reaction solution is poured into hot water under stirring, and the solvent is removed by stripping to recover the reaction solution; a method of directly heating the block copolymer solution and distilling off the solvent; etc.
Various stabilizers such as a phenol stabilizer, a phosphorus stabilizer, a sulfur stabilizer, and an amine stabilizer may be added to the hydrogenated product of the block copolymer.
The block copolymer of the present embodiment may have a "polar group" within a range that does not impair dielectric properties.
Examples of the "polar group" include, but are not limited to, a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acyl halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, a carboxylic acid ester group, an amide group, a sulfonic acid group, a sulfonate group, a phosphate group, an amino group, an imino group, a nitrile group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a thioether group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxy silicon group, a tin halide group, a boric acid group, a boron-containing group, a borate group, an alkoxy tin group, a phenyl tin group, and the like, and a group containing at least one of these functional groups.
The "polar group" described above may be formed using a modifier.
Examples of the modifier include, but are not limited to, tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-diaminomethylcyclohexane, epsilon-caprolactone, delta-valerolactone, 4-methoxybenzophenone, gamma-glycidoxyethyl trimethoxysilane, gamma-glycidoxypropyl dimethylphenoxy silane, bis (gamma-glycidoxypropyl) methylpropoxy silane, 1, 3-dimethyl-2-imidazolidinone, 1, 3-diethyl-2-imidazolidinone, N' -dimethylpropylurea, N-methylpyrrolidone, maleic acid, maleic anhydride imide, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, glycidyl methacrylate, crotonic acid, and the like.
As a method for forming the "polar group", a known method can be applied, and is not particularly limited.
Examples thereof include: a melt kneading method; a method of dissolving or dispersing each component in a solvent or the like and reacting the same; etc. In addition, there may be mentioned: a method of polymerizing by anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group; a method of modifying by subjecting a modifying agent having a functional group formed or contained at an active end to an addition reaction; a method in which an organic alkali metal compound such as an organolithium compound is reacted with a block copolymer (metallization reaction), and a modifier having a functional group is subjected to an addition reaction with a block polymer to which an organic alkali metal is added.
[ resin composition ]
The resin composition according to the present embodiment includes the block copolymer (component (I)) according to the present embodiment and at least one component selected from the group consisting of the following components (II) to (IV).
Component (II): free radical initiator
Component (III): polar resin (excluding component (I))
Component (IV): curing agent (excluding component (II))
From the viewpoints of lowering the dielectric constant, lowering the dielectric loss tangent, and flexibility of the resin composition and its cured product, the resin composition of the present embodiment preferably contains component (I): the above block copolymer and component (II): a free radical initiator.
Component (II) radical initiator
As the radical initiator, conventionally known ones can be used, and examples thereof include thermal radical initiators.
Examples of the thermal radical initiator include, but are not limited to, hydroperoxides such as dicumyl peroxide (Percumyl P), cumene hydroperoxide (Percumyl H), and tert-butyl hydroperoxide (PerbutylH); dialkyl peroxides such as α, α -bis (tert-butylperoxy-m-isopropyl) benzene (perbutyloxy P), dicumyl peroxide (Percumyl D), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (perhex a 25B), tert-butylcumyl peroxide (perbutyloxy C), di-tert-butylperoxide (perbutyloxy D), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne (Perhexyne 25B), tert-butyl peroxide (2-ethylhexanoate) (perbutyloxy O); peroxyketones; peroxy ketals such as n-butyl 4, 4-di (t-butylperoxy) valerate (PERHEXAV); diacyl peroxides; peroxydicarbonates; organic peroxides such as peroxyesters; azo compounds such as 2, 2-azobisisobutyronitrile, 1' - (cyclohexane-1-1-carbonitrile), 2' -azobis (2-cyclopropylpropionitrile), and 2,2' -azobis (2, 4-dimethylvaleronitrile); etc.
These may be used alone or in combination of 1 kind or 2 or more kinds.
(component (III)) polar resin
In order to impart properties such as adhesion to a predetermined substrate, the resin composition of the present embodiment may contain the component (III) in a range that does not impair the dielectric properties such as low dielectric constant and low dielectric loss tangent of the cured product: polar resin (excluding component (I)). By containing the polar resin, the resin composition of the present embodiment tends to have excellent adhesion to a predetermined substrate.
In the case where the component (III) is a polar resin having radical reactivity, the amount of the radical initiator of the component (II) may be arbitrarily adjusted depending on the reactivity, or the component (II) may not be added.
The polar resin having radical reactivity as the component (III) may be, for example, a homopolymer of a compound containing at least one vinyl group and/or halogen element in the polymer and/or a copolymer with an arbitrary compound. From the viewpoint of reactivity, it is preferable to have a vinyl group.
The polymer having a vinyl group may be a polymer composed of a repeating unit having a vinyl group, a polymer obtained by reacting a compound having a vinyl group and a polar group, or a polymer having a vinyl group obtained by reacting each polar group of a compound having a polar group.
Examples of the compound having a vinyl group and a polar group include carboxyl group-containing vinyl monomers such as (meth) acrylic acid (in this specification "(meth) acrylic acid" means methacrylic acid or acrylic acid), maleic acid, monoalkyl maleate, fumaric acid, and the like; vinyl monomers containing sulfone groups such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, and styrene sulfonic acid; hydroxyl group-containing vinyl monomers such as hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like; phosphate group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, phenyl-2-acryloyloxyethyl phosphate, and 2-acryloyloxyethyl phosphonic acid; hydroxyl-containing vinyl monomers such as hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, and 1-buten-3-ol; amino-containing vinyl monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like; amide group-containing vinyl monomers such as (meth) acrylamide, N-methyl (meth) acrylamide and N-butyl acrylamide; nitrile group-containing vinyl monomers such as (meth) acrylonitrile, cyanostyrene, and cyanoacrylate; epoxy group-containing vinyl monomers such as glycidyl methacrylate, tetrahydrofurfuryl (meth) acrylate, and p-vinylphenyl phenyl oxide.
Examples of the halogen element-containing compound include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.
Component (IV) curing agent
When the radical reactivity of the component (III) is low, the resin composition of the present embodiment preferably contains the component (IV): curing agent (excluding component (II)).
Component (IV): the curing agent generally has the following composition (III): the polar resin reacts to cure the resin composition.
The "reaction" of the component (III) with the component (IV) means that the polar groups of the respective components have covalent bonding property with each other. When the polar groups react with each other, for example, when OH of the carboxyl group is detached, the original polar groups change or disappear, and a covalent bond is formed, the definition that the polar groups show "reactivity" with each other is included.
From the aspect of curing function, component (IV): the curing agent preferably has at least 2 or more groups capable of reacting with the component (III) in 1 molecular chain: polar groups reacted by the functional groups of the polar resin.
The component (IV) may be used alone or in combination of 1 or more than 2.
The types of the polar groups contained in the component (III) and the component (IV) are not particularly limited, and examples thereof include:
epoxy and carboxyl, carbonyl, ester, imidazole, hydroxyl, amino, thiol, benzoxazine, carbodiimide, phenolic hydroxyl;
amino and carboxyl, carbonyl, hydroxyl, anhydride, sulfonic acid, aldehyde groups;
isocyanate groups, hydroxyl groups, carboxylic acids, phenolic hydroxyl groups;
anhydride groups and hydroxyl groups;
silanol groups and hydroxyl groups, carboxylic acid groups;
halo and carboxylic acid groups, carboxylate groups, amino groups, phenol groups, mercapto groups;
alkoxy and hydroxy, alkoxide groups, amino groups;
maleimide groups, cyanate groups, and the like.
Whether or not the polar groups are bonded to the component (III) or the component (IV) can be arbitrarily selected.
In addition, when the polar group of the component (III) and the polar group of the component (IV) do not react directly, the case where the polar group can react by adding a curing accelerator such as a catalyst is also included in the definition of "reactivity".
For example, when component (III) is a polar resin having an epoxy group and component (IV) is a curing agent having an acid anhydride group, the reactivity of the epoxy group with the acid anhydride group is usually very low, but by adding a compound having an amino group as a curing accelerator, the epoxy group of component (III) reacts with the amino group, and part or all of the epoxy group of component (III) becomes a hydroxyl group. Through the hydroxyl group and component (IV): the acid anhydride groups of the curing agent react, and the resin composition is cured.
From the aspect of reactivity, component (III): polar resin and component (IV): the amount ratio of the curing agent is preferably component (III) in terms of the molar ratio of the polar groups: component (IV) =1: 0.01 to 1: 20. more preferably 1:0.05 to 1: 15. further preferably 1:0.1 to 1:10.
component (IV): examples of the curing agent having an ester group include EXB9451, EXB9460, EXB, 9460S, HPC8000-65T, HPC H-65TM, EXB8000L-65TM, EXB8150-65T, EXB9416-70BK, manufactured by Mitsubishi chemical corporation, YLH1026, DC808, YLH1026, YLH1030, and YLH1048.
Examples of the curing agent having a hydroxyl group include MEH-7700, MEH-7810, MEH-7851, NHN, CBN, GPH manufactured by Japanese chemical Co., ltd., SN170, SN180, SN190, SN475, SN485, SN 495V, SN375, TD-2090 manufactured by DIC, LA-7052, LA-7054, LA-1356, LA-3018-50P, EXB-9500 and the like.
Examples of the curing agent having a benzoxazine group include ODA-BOZ manufactured by JFE chemical Co., ltd., HFB2006M manufactured by Showa polymer Co., ltd., and P-d and F-a manufactured by four-country chemical industry Co., ltd.
Examples of the curing agent having an isocyanate group include 2-functional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylidenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate phenyl-1- (methylethylidene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyanate phenyl) ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac and the like; prepolymers in which these cyanate ester resin moieties are triazinized; etc. Examples of the commercial products include PT30, PT60, ULL-950S, BA, and BA230S75 manufactured by Lonza Japan.
Examples of the curing agent having a carbodiimide group include V-03 and V-07 manufactured by Nisshink chemical Co.
As the curing agent having an amino group, there is used, examples thereof include 4,4' -methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyl toluenediamine, 4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Examples of the commercial products include KAYABOND C-200S, KAYABOND C-100, KAYAHARD A-A, KAYAHARD A-B, KAYAHARD A-S, and Epicure W manufactured by Mitsubishi chemical corporation.
In addition, from the viewpoint of reactivity, the amino group is preferably a primary amine and/or a secondary amine, and more preferably a primary amine.
Examples of the curing agent having an acid anhydride group include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnorbornene dianhydride, hydrogenated methylnorbornene dianhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, and polymer-type acid anhydrides such as 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthol [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride), styrene-maleic resin obtained by copolymerizing styrene and maleic acid.
In addition, the compound having at least 2 of the above structures having radical reactivity also has a function of reacting with the component (III) to cure the resin composition. The compound can also be used as a curing agent for the component (IV).
Examples of the compound having at least 2 structures having radical reactivity include allyl monomers such as triallyl isocyanurate (TAIC manufactured by mitsubishi chemical company), tris (2-hydroxyethyl) isocyanurate, diallyl fumarate, diallyl adipate, triallyl citrate, diallyl hexahydrophthalate, and the like.
When the resin composition of the present embodiment contains the component (III), the component (III) is as follows: the polar resin is preferably at least one selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, liquid crystal polyester resins, and fluorine resins in view of adhesion. More preferably at least 1 selected from the group consisting of epoxy resins, polyimide resins, and polyphenylene ether resins.
The polyimide-based resin as the component (III) may be any resin having an imide bond in a repeating unit and falling within the category called polyimide resins. For example, a general polyimide structure obtained by polycondensing a tetracarboxylic acid or a dianhydride thereof with a diamine (forming an imide bond) is given. From the viewpoint of curability, it is preferable that the terminal of the polyimide structure has an unsaturated group. Examples of the polyimide resin having an unsaturated group at the terminal include maleimide-type polyimide resins, nadic imide-type polyimide resins, and allylnadic imide-type polyimide resins.
Examples of the tetracarboxylic acid or dianhydride thereof include, but are not limited to, aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride, and the like. The number of these may be 1 alone or 2 or more.
The diamine is not particularly limited, and examples thereof include aromatic diamines, alicyclic diamines, aliphatic diamines, and the like which are generally used for the synthesis of polyimide. The number of these may be 1 alone or 2 or more.
In addition, from the viewpoint of lowering the dielectric constant and lowering the dielectric loss tangent, at least one of the tetracarboxylic acid, dianhydride thereof, and diamine may have 1 or more functional groups selected from the group consisting of fluoro group, trifluoromethyl group, hydroxyl group, sulfone group, carbonyl group, heterocycle, long-chain alkyl group, allyl group, and the like.
As the polyimide resin of the component (III), a commercially available polyimide resin can be used, examples thereof include Neoprim (registered trademark) C-3650 (Mitsubishi gas chemical Co., ltd., trade name), neoprim C-3G30 (Mitsubishi gas chemical Co., ltd., trade name), neoprim C-3450 (Mitsubishi gas chemical Co., ltd., trade name), neoprim P500 (Mitsubishi gas chemical Co., ltd., trade name), BT (bismaleimide triazine) resin (Mitsubishi gas chemical Co., ltd.), JL-20 (New Japanese chemical manufacturing trade name) (silicon oxide may be contained in the varnish of these polyimide resins), RIKACOAT SN20 (New Japanese chemical Co., ltd.) RIKACOAT PN20, pyr-ML manufactured by I.S.T., UPIA-AT manufactured by Yu Xingzhi Co., ltd., UPIA-ST, UPIA-NF, UPIA-LB, PIX-1400 manufactured by Hitachi chemical Co., ltd., PIX-3400, PI2525, PI2610, HD-3000, AS-2600, HPC-5000 manufactured by Showa electric Co., ltd., HPC-5012, HPC-1000, HPC-5020, HPC-3010, HPC-6000, HPC-9000, HCI-7000, HCI-1000S, HCI-1200-E, HCI-1300, BMI-2300 manufactured by Dai chemical Co., ltd., and MIR-3000 manufactured by Xin Japanese chemical Co., ltd.
The polyphenylene ether resin as the component (III) may be any resin as long as it falls within the category called polyphenylene ether resins, and contains a phenylene ether unit as a repeating structural unit. In addition, other structural units than the phenylene ether unit may be contained.
As the homopolymer having a phenylene ether unit, whether or not the phenylene group in the phenylene unit has a substituent is not particularly limited. Examples of the substituent include: acryl groups such as ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; cyclic alkyl groups such as cyclohexyl; unsaturated bond-containing substituents such as vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, p-vinylphenyl, p-isopropenylphenyl, m-vinylphenyl, m-isopropenylphenyl, o-vinylphenyl, o-isopropenylphenyl, p-vinylbenzyl, p-isopropenylbenzyl, m-vinylbenzyl, m-isopropenylbenzyl, o-vinylbenzyl, p-vinylphenylvinyl, p-vinylphenylpropenyl, p-vinylphenylbutenyl, m-vinylphenylvinyl, m-vinylphenylpropenyl, m-vinylphenylbutenyl, o-vinylphenylvinyl, o-vinylphenylbutenyl, methacryloyl, acryl, 2-ethylpropoyl, 2-hydroxymethylpropoyl and the like; functional group-containing substituents such as hydroxyl, carboxyl, carbonyl, thiocarbonyl, acyl halide, anhydride, carboxylic acid, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylic ester, amide, sulfonic acid, sulfonate, phosphate, amino, imino, nitrile, pyridyl, quinolinyl, epoxy, thiocpoxy, thioether, isocyanate, isothiocyanate, silicon halide, silanol, silicon alkoxide, tin halide, boric acid, boron-containing, borate, tin alkoxide, and tin phenyl. From the viewpoint of curability, it is preferable to have an arbitrary polar group for the purpose of having radical reactivity and/or reactivity with the component (IV) curing agent.
The molecular weight of the polyphenylene ether resin as the component (III) is preferably 100000 or less, more preferably 50000 or less, and further preferably 10000 or less in view of curability of the resin composition of the present embodiment. The polyphenylene ether resin may be linear or may have a crosslinked or branched structure.
The liquid crystal polyester resin as the component (III) is a polyester forming an anisotropic melt phase, and may be a category called liquid crystal polyester resin.
Examples thereof include "X7G" manufactured by Izeman Kodak corporation, xydar manufactured by the company of Duchesnea コ, EKONOL manufactured by the company of Sumitomo chemistry, and Vectra manufactured by the company of Seranis.
The fluorine-based resin as the component (III) may be an olefin-based polymer containing a fluorine group as long as it falls into the category called fluorine resins.
Examples of the fluorine-based resin include polytetrafluoroethylene, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, perfluoroethylene-propylene copolymer, polyvinylidene fluoride, polytrifluoroethylene, and ethylene-chlorotrifluoroethylene copolymer.
The epoxy resin as the component (III) may be any epoxy resin as long as it is a category called epoxy resin, and it is preferable that the epoxy resin has 2 or more epoxy groups in 1 molecule from the viewpoint of strength.
The epoxy resin may be used alone or in combination of 2 or more.
Examples of the epoxy resin include: a xylenol-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol novolac-type epoxy resin, a phenol novolac-type epoxy resin, a tert-butyl-catechol-type epoxy resin, a naphthalene-type epoxy resin, a naphthol-type epoxy resin, an anthracene-type epoxy resin, a glycidylamine-type epoxy resin, a glycidyl ester-type epoxy resin, a cresol novolac-type epoxy resin, a biphenyl-type epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro-ring-containing epoxy resin, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a naphthylene ether-type epoxy resin, a trimethylol-type epoxy resin, a tetraphenylethane-type epoxy resin, and the like.
In addition, in terms of reactivity, when an epoxy resin is used as the component (III), it is preferable to contain the component (IV) curing agent together, and in this case, examples of the polar groups contained in the component (IV) curing agent include carboxyl groups, imidazolyl groups, hydroxyl groups, amino groups, thiol groups, benzoxazinyl groups, and carbodiimide groups, and in terms of reactivity, carboxyl groups, imidazolyl groups, hydroxyl groups, benzoxazinyl groups, and carbodiimide groups are preferable, and in terms of dielectric properties, hydroxyl groups, carboxyl groups, imidazolyl groups, benzoxazinyl groups, and carbodiimide groups are more preferable, and hydroxyl groups, carboxyl groups, and carbodiimide groups are further preferable.
In the case of using 2 or more polar resins having different radical reactivity as component (III), component (II) is preferably used in combination in terms of curability: radical initiator and component (IV): and (3) a curing agent. For example, when a maleimide-based polyimide resin having excellent radical reactivity and a bisphenol a epoxy resin having no radical reactivity are used as the component (III), the above-mentioned component (II) radical initiator and the above-mentioned component (IV) curing agent are preferably added in view of curability.
In addition, in the case of using a polar resin having a high melting point and high rigidity as the component (III): in the case of the polar resin, the resin composition of the present embodiment may not contain the component (IV). Examples of the resin having a high melting point and high rigidity of the component (III) include liquid crystal polyester resins and fluorine resins such as polytetrafluoroethylene.
By setting the component (III) to have a high melting point and high rigidity, the strength required for practical use tends to be able to be obtained even when the component (IV) is not contained.
Component (V) additives
The resin composition of the present embodiment may further contain various additives such as a curing accelerator, a filler, and a flame retardant as component (V).
The component (V) contained in the additive as the block copolymer of the component (I) is the same as the component (V) of the resin composition.
The curing accelerator is added to promote the reactivity between the above components, and conventionally known curing accelerators can be used. Examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like.
The curing accelerator may be used alone or in combination of at least 2 kinds.
Examples of the phosphorus-based curing accelerator include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphine and tetrabutylphosphonium decanoate.
Examples of the amine-based curing accelerator include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5, 4, 0) -undecene, and the like, and 4-dimethylaminopyridine and 1, 8-diazabicyclo (5, 4, 0) -undecene are preferable.
As the imidazole-based curing accelerator, there is used, examples thereof include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, and, 2-phenylimidazole isocyanuric acid adduct, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and the like, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole.
As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include P200-H50 manufactured by Mitsubishi chemical corporation.
Examples of the guanidine-based curing accelerator include, but are not limited to, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like, and dicyandiamide and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferable.
Examples of the metal-based curing accelerator include, but are not limited to, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
Specific examples of the organometallic complex include cobalt (II) acetylacetonate, cobalt (III) acetylacetonate and other organic cobalt complexes, copper (II) acetylacetonate and other organic copper complexes, zinc (II) acetylacetonate and other organic zinc complexes, iron (III) acetylacetonate and other organic iron complexes, nickel (II) acetylacetonate and other organic nickel complexes, manganese (II) acetylacetonate and other organic manganese complexes.
Specific examples of the organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the filler include, but are not limited to: inorganic fillers such as silica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fibers, glass beads, glass hollow spheres, glass flakes, graphite, titanium oxide, potassium titanate whiskers, carbon fibers, alumina, kaolin, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconia, potassium titanate, alumina, and metal particles; wood chips, wood powder, pulp, cellulose nanofibers, and the like.
These fillers may be used alone in an amount of only 1, or in combination of plural types.
The shape of these fillers may be any of scaly, spherical, granular, powder, amorphous, and the like, and is not particularly limited.
In many cases, the resin composition or the cured product of the present embodiment is exposed to high temperature during molding or the like, and the filler preferably has a small linear expansion coefficient in order to prevent shrinkage due to temperature change and deformation of the molded product. From the viewpoint of reducing the linear expansion coefficient, the filler is preferably silicon oxide, and examples of the silicon oxide include amorphous silicon oxide, fused silicon oxide, crystalline silicon oxide, synthetic silicon oxide, hollow silicon oxide, and the like.
Examples of the flame retardant include, but are not limited to, halogen flame retardants such as bromine compounds, phosphorus flame retardants such as aromatic compounds, metal hydroxides, alkyl sulfonates, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, hexabromobenzene, decabromodiphenylethane, 4-dibromobiphenyl, ethylene bis-tetrabromophthalimide, and other flame retardants containing aromatic bromine compounds.
These flame retardants are used singly or in combination of 2 or more.
The flame retardant also includes a so-called flame retardant auxiliary which exhibits a more excellent effect synergistically by being used in combination with other flame retardants, although the flame retardancy of the flame retardant itself is low.
The filler and the flame retardant may be of a type which has been subjected to a surface treatment in advance with a surface treatment agent such as a silane coupling agent.
Examples of the surface treating agent include, but are not limited to, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. They may be used singly or in combination of plural kinds.
The other additives are not particularly limited as long as they are additives generally used for compounding a resin composition and/or a cured product.
Examples of the other additives include, but are not limited to: pigments and/or colorants such as carbon black and titanium oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bis-stearamide, and the like; an anti-sticking agent; plasticizers such as organopolysiloxanes, fatty acid esters such as phthalate compounds and adipate compounds, azelate compounds, and mineral oil; antioxidants such as hindered phenol-based and phosphorus-based heat stabilizers; hindered amine light stabilizers; benzotriazole-based ultraviolet absorbers; an antistatic agent; an organic filler; a thickener; a defoaming agent; a leveling agent; resin additives such as adhesion imparting agents; other additives or mixtures of these, etc.
From the viewpoints of the low dielectric constant and low dielectric loss tangent, the resin composition of the present embodiment preferably does not contain pigments, colorants, lubricants, anti-blocking agents, and antistatic agents.
The resin composition in the present embodiment may be a melt-kneaded product of each component, or may be a product obtained by dissolving each component in a soluble solvent and stirring the mixture (hereinafter referred to as "varnish"), and a varnish is preferable from the viewpoint of handling properties.
Examples of the solvent include, but are not limited to: ketones such as acetone, methyl Ethyl Ketone (MEK), cyclohexanone, and γ -butyrolactone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and diethylene glycol-diethyl ether monoacetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of at least 2 kinds.
[ cured product ]
The cured product of the present embodiment contains the block copolymer of the present embodiment described above.
The cured product of the present embodiment is obtained by subjecting the resin composition of the present embodiment to a curing reaction at an arbitrary temperature and time. The term "cured product" is intended to include not only a completely cured product but also a system (semi-cured) in which only a part of the resin composition is cured and an uncured component is contained.
In the production process of the laminate described later, a step of further curing the cured product may be performed.
The reaction temperature in the curing step of the cured product of the present embodiment is preferably 80℃or higher, more preferably 100℃or higher, and still more preferably 120℃or higher. The reaction time is preferably 10 to 240 minutes, more preferably 20 to 230 minutes, and still more preferably 30 to 220 minutes. When the resin composition of the present embodiment is a varnish, the curing reaction is preferably performed after the solvent is removed. The drying method may be carried out by a conventionally known method such as heating or hot air blowing, and is preferably carried out at a temperature lower than the curing reaction temperature, and the amount of the solvent in the resin composition is preferably 10 mass% or less, more preferably 5 mass% or less.
[ resin film ]
The resin film of the present embodiment is composed of the resin composition of the present embodiment.
The resin film of the present embodiment is obtained by: the varnish comprising the resin composition of the present embodiment is spread in a uniform film form on an appropriate support, and the solvent is removed by drying as described above. The resin film may be wound into a roll and stored.
The resin film of the present embodiment may be formed by laminating a predetermined protective film, and in this case, the protective film may be peeled off for use.
Examples of the support include a film made of a plastic material, a metal foil, and a release paper.
As the film made of a plastic material of the support, there may be mentioned, for example, but not limited to: polyesters such as polyethylene terephthalate and polyethylene naphthalate; acrylic such as polycarbonate and polymethyl methacrylate (PMMA); cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like, and polyethylene terephthalate and polyethylene naphthalate are preferable from the viewpoints of availability and cost.
Examples of the metal foil include, but are not limited to, copper foil, aluminum foil, and the like, and copper foil is preferable. As the copper foil, a foil composed of a single metal of copper or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The support may be subjected to roughening treatment, corona treatment, antistatic treatment, and anti-sticking treatment on the surface to be bonded to the resin composition layer.
[ prepreg ]
The prepreg of the present embodiment includes a base material and the resin composition of the present embodiment impregnated into or applied to the base material. That is, the prepreg according to the present embodiment is a composite of the resin composition according to the present embodiment and the base material.
The prepreg is obtained, for example, by: the base material such as glass cloth is impregnated with the varnish as the resin composition of the present embodiment, and then the solvent is removed by the drying method described above, thereby obtaining the resin composition.
Examples of the substrate include, but are not limited to: various glass cloths such as coarse gauze, cloth, chopped strand mats, surface mats and the like; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; woven or nonwoven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, flax cloth and felt; natural cellulose base materials such as carbon fiber cloth, kraft paper, cotton paper, and cloth obtained from paper-glass mixed filaments; porous polytetrafluoroethylene film, etc., glass cloth is preferable in terms of dielectric properties.
These substrates may be used singly or in combination of 2 or more.
The proportion of the solid component composed of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the ratio is 30% by mass or more, the insulating reliability tends to be more excellent when the prepreg is used for an electronic substrate or the like. When the ratio is 80 mass% or less, mechanical properties such as rigidity tend to be more excellent in applications such as electronic substrates.
[ laminate ]
The laminate of the present embodiment includes the resin film and the metal foil. The laminate of the present embodiment includes the cured product of the prepreg and a metal foil.
The laminate of the present embodiment can be produced, for example, by the following steps: a step (a) of laminating a resin film composed of the resin composition of the present embodiment on a substrate to form a resin layer, thereby obtaining a prepreg; a step (b) of heating and pressurizing the resin layer to planarize the resin layer, thereby obtaining a cured product of the prepreg; and a step (c) of further forming a predetermined wiring layer made of a metal foil on the resin layer; etc.
In the step (a), the method of laminating the resin film on the substrate is not particularly limited, and examples thereof include a multi-stage press, a vacuum press, an atmospheric pressure laminator, a method of laminating using a laminator heated and pressurized under vacuum, and the like, and a method of using a laminator heated and pressurized under vacuum is preferable. In the method using the laminator, even if the target electronic circuit board has a fine wiring circuit on the surface, the inter-circuit can be buried with resin without a void. The lamination may be performed in a batch type or a continuous type using a roll or the like.
Examples of the base material include, but are not limited to, various base materials constituting the prepreg, and for example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, polyphenylene oxide substrates, and fluororesin substrates. The surface of the laminated resin layer of the base material may be roughened in advance, and the number of layers of the base material is not limited.
In the step (b), the resin film and the base material laminated in the step (a) are heated and pressurized to planarize the resin film and the base material. The conditions may be arbitrarily adjusted depending on the kind of the base material and the composition of the resin film, and for example, the temperature is preferably in the range of 100 to 300 ℃, the pressure is preferably in the range of 0.2 to 20MPa, and the time is preferably in the range of 30 to 180 minutes.
In the step (c), the resin film and the base material are heated and pressurized, and a predetermined wiring layer made of a metal foil is further formed on the produced resin layer. The forming method is not particularly limited, and conventionally known methods may be used, and examples thereof include etching methods such as subtractive method and semi-additive method.
The subtractive method is as follows: a resist layer having a shape corresponding to a desired pattern shape is formed on the metal layer, and then the metal layer from which the resist has been removed is dissolved and removed with a reagent by a subsequent development treatment, thereby forming a desired wiring.
The semi-addition method comprises the following steps: a metal film is formed on the surface of a resin layer by electroless plating, a plating resist layer having a shape corresponding to a desired pattern is formed on the metal film, and then a metal layer is formed by electroplating, and then unnecessary electroless plating is removed by a reagent or the like to form a desired wiring layer.
The resin layer may be formed with holes such as via holes as needed, and the method for forming the holes is not particularly limited, and conventionally known methods may be used. As a hole forming method, for example, NC drill, carbon dioxide laser, UV laser, YAG laser, plasma, or the like can be used.
[ Metal-clad laminate ]
The laminate of the present embodiment may be plate-shaped or flexible.
The laminate of the present embodiment may be a metal-clad laminate.
The metal-clad laminate is obtained by laminating and curing the resin composition of the present embodiment or the prepreg of the present embodiment with a metal foil, and a part of the metal foil is removed from the metal-clad laminate.
The metal-clad laminate preferably has a form in which a cured product of a prepreg (also referred to as a "cured product composite") is laminated and adhered to a metal foil, and is suitably used as a material for an electronic circuit board.
Examples of the metal foil include, but are not limited to, aluminum foil and copper foil, and copper foil is preferable because of low resistance.
The cured product of the prepreg combined with the metal foil may be 1 sheet or a plurality of sheets, and the metal foil may be laminated on one or both sides of the cured product according to the application, and processed into a laminate.
Examples of the method for producing the laminated board include the following methods: a prepreg comprising the resin composition of the present embodiment and a base material is formed, and after being laminated with a metal foil, the resin composition is cured, whereby a laminate of a cured product of the prepreg and the metal foil is obtained.
One of the particularly preferred uses of the laminate is a printed circuit board. The printed circuit board preferably removes at least a portion of the metal foil from the metal-clad laminate.
The printed wiring board may be manufactured by a press-heating molding method using the prepreg according to the present embodiment. As the base material, the same base materials as those described for the prepreg above can be used. The printed wiring board has excellent strength and electrical characteristics (low dielectric constant and low dielectric loss tangent), and further, can suppress variation in electrical characteristics accompanying environmental variation, and has excellent insulation reliability and mechanical characteristics by including the resin composition of the present embodiment.
[ Material for electronic Circuit Board ]
The material for the electronic circuit board of the present embodiment contains the cured product of the resin composition of the present embodiment.
The material for the electronic circuit board of the present embodiment can be produced using the resin composition and/or varnish of the present embodiment described above.
The material for an electronic circuit board of the present embodiment includes at least one selected from the group consisting of a cured product of the above-described resin composition, a resin film containing the resin composition of the present embodiment or a cured product thereof, and a composite prepreg of a base material and the resin composition. The material for the electronic circuit board of the present embodiment can be used as a printed circuit board provided with a metal foil with a resin.
Examples
The present embodiment will be specifically described below with reference to specific examples and comparative examples, but the present invention is not limited to the examples and comparative examples.
The methods for identifying the structure and measuring the physical properties of the block copolymer (component (I)) used in the examples and comparative examples below are as follows.
[ method for identifying Polymer Structure and measuring physical Properties ]
((1) content of vinyl aromatic monomer units of Block copolymer)
The content of the vinyl aromatic monomer unit in the block copolymer was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu corporation, UV-2450) using the block copolymer before hydrogenation.
((2) vinyl bond content of Block copolymer)
The vinyl bond content was measured using an infrared spectrophotometer (FT/IR-230, manufactured by Japanese Spectroscopy Co., ltd.) using the block copolymer before hydrogenation.
The vinyl bond content of the block copolymer was calculated by the hamilton method.
This value is taken as the content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding in the case where the total content of the polymer block (B) and/or the polymer block (C) of the component (I) block copolymer is 100%.
((3) molecular weight and molecular weight distribution of Block copolymer)
Using GPC [ apparatus: LC-10 (manufactured by shimadzu corporation), column: TSKgel GMHXL (4.6 mm. Times.30 cm) ] the molecular weight of the block copolymer of component (I) before modification and before hydrogenation was measured.
Tetrahydrofuran was used as the solvent. With respect to the measurement conditions, the measurement was performed at a temperature of 35 ℃.
The molecular weight is a weight average molecular weight obtained by obtaining the molecular weight of the peak of the chromatogram using a calibration curve obtained by measuring a commercially available standard polystyrene (prepared using the peak molecular weight of the standard polystyrene).
When a plurality of peaks are present in the chromatogram, the molecular weight is an average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram).
The molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained.
((4) hydrogenation Rate of double bonds of conjugated diene monomer units of Block copolymer)
The hydrogenated block copolymer of component (I) was used, and the hydrogenation ratio of the double bonds of the conjugated diene monomer units was measured by using a nuclear magnetic resonance apparatus (DPX-400, manufactured by BRUKER Co.).
[ Block copolymer, material of resin composition ]
(preparation of hydrogenation catalyst)
In examples and comparative examples described below, hydrogenation catalysts used in producing block copolymers were prepared by the following methods.
A reaction vessel equipped with a stirring device was replaced with nitrogen, and 1 liter of dried and purified cyclohexane was charged therein.
Then 100 mmol of bis (. Eta.5-cyclopentadiene) titanium dichloride was added. While stirring the mixture well, a 200 mmol solution of trimethylaluminum in n-hexane was added thereto, and the mixture was allowed to react at room temperature for about 3 days. Thus, a hydrogenation catalyst was obtained.
Component (I) block copolymer
The block copolymer of the vinyl aromatic compound and the conjugated diene was prepared as follows.
The structure and physical properties of each block copolymer are shown in tables 1 and 2.
In the table, (a) represents a polymer block (a) mainly composed of vinyl aromatic monomer units, (B) represents a polymer block (B) mainly composed of conjugated diene monomer units, and (C) represents a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units.
< Block copolymer (1) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 37.5 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged into the above-mentioned tank reactor.
Next, 0.23 parts by mass of n-butyllithium and 0.8 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 45 minutes.
Subsequently, a cyclohexane solution (concentration: 20 mass%) containing 25 parts by mass of butadiene was added, and the mixture was polymerized at 70℃for 20 minutes.
Then, 37.5 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged, and polymerization was conducted for 45 minutes. Then methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer.
The block copolymer obtained as described above had a styrene content of 75% by mass and a weight average molecular weight of 3.0X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 70%.
< Block copolymer (2) >
Polymerization was carried out in the same manner as in the block copolymer (1) above except that 0.36 parts by mass of n-butyllithium was added to 100 parts by mass of the whole monomers.
The block copolymer obtained as described above had a styrene content of 75 mass% and a weight average molecular weight of 2.1X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 70%.
< Block copolymer (3) >
Polymerization was carried out in the same manner as in the block copolymer (1) except that 0.65 parts by mass of n-butyllithium and 1.2 m/1 tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers.
The block copolymer obtained as described above had a styrene content of 75% by mass and a weight average molecular weight of 1.0X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 71%.
< Block copolymer (4) >
Polymerization was carried out in the same manner as in the block copolymer (3) except that 1.42 parts by mass of n-butyllithium was added to 100 parts by mass of the whole monomers.
The block copolymer obtained as described above had a styrene content of 75% by mass and a weight average molecular weight of 0.5X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 69%.
< Block copolymer (5) >
Polymerization was carried out in the same manner as in the block copolymer (3) except that 3.20 parts by mass of n-butyllithium was added to 100 parts by mass of the whole monomers.
The block copolymer (5) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 0.2X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 70%.
< Block copolymer (6) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 27.5 parts by mass of styrene was charged into the above-mentioned tank reactor.
Then, 1.42 parts by mass of n-butyllithium and 1.2 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 45 minutes.
Then, 45 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing butadiene was added thereto, and the mixture was polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 27.5 parts by mass of styrene was charged and polymerized for 45 minutes. Then methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer.
The block copolymer (6) obtained as described above had a styrene content of 55% by mass and a weight-average molecular weight of 0.5X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 69%.
< Block copolymer (7) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 45 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged into the tank reactor.
Then, 1.42 parts by mass of n-butyllithium and 1.2 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 45 minutes.
Next, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of butadiene was added, and polymerization was carried out at 70℃for 20 minutes.
Then, 45 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged, and polymerization was conducted for 45 minutes. Then methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer.
The block copolymer (7) obtained as described above had a styrene content of 90% by mass and a weight average molecular weight of 0.5X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 70%.
< Block copolymer (8) >
Polymerization was carried out in the same manner as in the block copolymer (4) above except that 0.1 ml of TMEDA was added to 1 ml of n-butyllithium.
The block copolymer (8) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 0.5X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond content: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 31%.
< Block copolymer (9) >
Polymerization was carried out in the same manner as in the block copolymer (8) except that 0.1 ml of TMEDA was added to 1 ml of n-butyllithium to extend the polymerization time of each block by 5 minutes.
The block copolymer (9) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 0.5X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 16%.
< hydrogenated Block copolymer (10) >)
The same polymerization operation as in the block copolymer (4) was carried out. Thereafter, 90ppm of the hydrogenation catalyst prepared as described above based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 0.15 hours to obtain a hydrogenated block copolymer (10).
The hydrogenated block copolymer (10) obtained as described above had a styrene content of 75% by mass and a weight average molecular weight of 0.5X10 4 The content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: unit (a)/polymer block (B)) was 1.10, and the hydrogenation rate was 22%.
< hydrogenated Block copolymer (11) >)
The hydrogenation reaction was carried out for 0.35 hour, and the same operation as that of the above-mentioned hydrogenated block copolymer (10) was carried out to obtain a hydrogenated block copolymer (11).
The hydrogenated block copolymer (11) obtained as described above had a styrene content of 75% by mass and a weight average molecular weight of 0.5X10 4 Content of units (a) having a molecular weight distribution of 1.10 and originating from 1, 2-and/or 3, 4-linkagesVinyl bond amount: the unit (a)/polymer block (B)) was 69% and the hydrogenation rate was 51%.
< hydrogenated Block copolymer (12) >)
The hydrogenation reaction was carried out for 0.75 hour, and the same operation as that of the above-mentioned hydrogenated block copolymer (10) was carried out to obtain a hydrogenated block copolymer (12).
The hydrogenated block copolymer (12) obtained as described above had a styrene content of 75% by mass and a weight average molecular weight of 0.5X10 4 The content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: unit (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 71%, and the hydrogenation rate was 72%.
< Block copolymer (13) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 30 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged into the tank reactor.
Subsequently, 1.42 parts by mass of n-butyllithium and 1.2 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 25 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 15 parts by mass of styrene and 25 parts by mass of butadiene was added, and the mixture was polymerized at 70℃for 35 minutes.
Then, 30 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged, and polymerization was carried out for 25 minutes. Thereafter, methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer (13).
The block copolymer (13) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 0.5X10 4 The content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: unit (a)/conjugated diene monomer unit amount in the polymer block (C)) having a molecular weight distribution of 1.10 was 69%.
< Block copolymer (14) >
2.0mol of TMEDA was added to n-butyllithium to give a reaction temperature of 50℃andThe same procedure as for the block copolymer (3) was carried out except that the reaction time of each block was prolonged by 20 minutes, to obtain a block copolymer (14). The resulting block copolymer (14) had a styrene content of 75% by mass and a weight-average molecular weight of 1.0X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond content: units (a)/polymer block (B)) having a molecular weight distribution of 1.13 was 88%.
< Block copolymer (15) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 25 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged.
Then, 0.45 parts by mass of n-butyllithium and 0.8 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 50 parts by mass of styrene and 25 parts by mass of butadiene was added, and the mixture was polymerized at 70℃for 30 minutes.
Thereafter, methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer (15).
The block copolymer (15) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 1.5X10 4 The content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: unit (a)/conjugated diene monomer unit amount in the polymer block (C)) having a molecular weight distribution of 1.10 was 71%.
< Block copolymer (16) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 22.5 parts by mass of styrene was charged into the above-mentioned tank reactor.
Next, 0.65 parts by mass of n-butyllithium and 1.2 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 15 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 55 parts by mass of butadiene was added, and the mixture was polymerized at 70℃for 30 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 22.5 parts by mass of styrene was charged, and polymerization was carried out for 20 minutes. Thereafter, methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer (16).
The block copolymer (16) obtained as described above had a styrene content of 45% by mass and a weight average molecular weight of 1.0X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 71%.
< Block copolymer (17) >
The same procedure as for the block copolymer (3) was conducted except that 0.17 parts by mass of n-butyllithium was used per 100 parts by mass of the whole monomers, to obtain a block copolymer (17).
The block copolymer (17) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 4.0X10 4 The content of units (a) originating from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: units (a)/polymer block (B)) having a molecular weight distribution of 1.10 was 71%.
< Block copolymer (18) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 7.5 parts by mass of butadiene was charged into the tank reactor.
Next, 0.65 parts by mass of n-butyllithium and 1.2 m/l of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 5 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of butadiene and 75 parts by mass of styrene was added, and the mixture was polymerized at 70℃for 30 minutes.
Next, a cyclohexane solution (concentration: 20 mass%) containing 7.5 parts by mass of butadiene was charged, and polymerization was conducted for 5 minutes. Thereafter, methanol was added to stop the polymerization reaction, thereby obtaining a block copolymer (18).
The block copolymer (18) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 1.0X10 4 The content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: unit (a)/(amount of conjugated diene monomer unit in polymer block (B) +polymer block (C)) having a molecular weight distribution of 1.10 was 70%.
< Block copolymer (19) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 25 parts by mass of butadiene and 75 parts by mass of styrene was charged into the tank reactor.
Subsequently, 1.42 parts by mass of n-butyllithium and 1.2 m/ml of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 60 minutes to obtain a block copolymer (19).
The block copolymer (19) obtained as described above had a styrene content of 75% by mass and a weight-average molecular weight of 1.0X10 4 The content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding (vinyl bond amount: unit (a)/conjugated diene monomer unit amount in the block (C)) having a molecular weight distribution of 1.10 was 70%.
Component (II) radical initiator
Perbutyl C (manufactured by Nipple Co., ltd.)
Percumyl D (manufactured by Nipple Co., ltd.)
(component (III)) polar resin
As the polar resin, a polyphenylene ether resin (PPE) was polymerized as follows.
To a 1.5 liter jacketed reactor equipped with a nozzle for introducing an oxygen-containing gas, stirring turbine blades and a baffle at the bottom of the reactor, 180.0g of 2, 6-dimethylphenol containing 5 m/l% of 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, and containing 0.2512g of copper chloride dihydrate, 1.1062g of 35% hydrochloric acid, 3.6179g of di-N-butylamine, 9.5937g of N, N, N ', N' -tetramethylpropanediamine, 211.63g of methanol and 493.80g of N-butanol were added, and a reflux cooler was provided in the exhaust line at the upper part of the reactor.
The composition mass ratio of the used solvent is n-butanol: methanol=70: 30. next, oxygen was introduced from a nozzle to the reactor at a rate of 180mL/min while vigorously stirring, and the polymerization temperature was kept at 40℃while introducing a heat medium into the jacket, thereby adjusting the temperature.
The polymerization solution gradually becomes slurry.
After the polyphenylene ether reached the desired number average molecular weight, aeration of the oxygen-containing gas was stopped, and the resulting polymerization mixture was heated to 50 ℃. Then, hydroquinone (and a reagent manufactured by Wako pure chemical industries, ltd.) was added little by little, and the temperature was kept at 50℃until the slurry-like polyphenylene ether became white.
Subsequently, 720g of a methanol solution containing 6.5 mass% of 36% hydrochloric acid was added thereto, followed by filtration and repeated washing with methanol to obtain a wet polyphenylene ether.
Then, the mixture was dried in vacuo at 100℃to obtain a dried polyphenylene ether. The ηsp/c was 0.103dL/g, and the yield was 97%.
In the measurement of ηsp/c, the above-mentioned polyphenylene ether was prepared into a chloroform solution of 0.5g/dL, and the reduced viscosity (. Eta.sp/c) at 30℃was determined by using an Ubbelohde viscosity tube. The unit is dL/g.
The obtained polyphenylene ether was modified as follows.
152.5g of polyphenylene ether and 152.5g of toluene were mixed and heated to about 85 ℃. Then, 2.1g of dimethylaminopyridine was added. 18.28g of methacrylic anhydride was slowly added at the moment the solid was completely dissolved. The resulting solution was continuously mixed while maintaining at 85 ℃ for 3 hours. Then, the solution was cooled to room temperature to obtain a toluene solution of the methacrylate-capped polyphenylene ether. To the toluene solution thus obtained, 1000mL of methanol at 10℃was dropwise added to a cylindrical 3L SUS container with a homogenizer stirred. The resulting powder was filtered, washed with methanol and dried at 85℃under nitrogen for 18 hours.
Component (IV) curing agent
Triallyl isocyanurate (TAIC) TM ) (Mitsubishi chemical Co., ltd.)
[ method for measuring physical Properties of resin composition ]
((1) dielectric loss tangent and permittivity)
Dielectric loss tangent at 10GHz was measured by cavity resonance method.
As the measurement device, a network analyzer (manufactured by N5230A, agilentTechnologies corporation) and a cavity resonator (Cavity Resornator CP series) manufactured by kanto electronic application development corporation were used.
For the measurement sample, a test piece having a width of 2.6mm×a length of 80mm was cut from a cured film described later, and this was used as the measurement sample.
Using the dielectric loss tangent and the dielectric constant obtained above, the following examples and comparative examples were evaluated according to the following criteria.
Evaluation criterion in examples 1 to 17 and comparative examples 1 to 7
Dielectric loss tangent
And (3) the following materials: below 0.004
O: 0.005 or less
Delta: less than 0.006
X: 0.006 or more
Dielectric constant
And (3) the following materials: 2.23 or less
O: 2.27 or less
Delta: less than 2.30
X: 2.30 or more
Evaluation criterion in examples 18 to 27 and comparative examples 8 to 18
Evaluation was performed by using the difference between the dielectric loss tangent and the dielectric constant of comparative example 8, which does not contain a block copolymer, and that of each example or comparative example (comparative example 8-example or comparative example).
Dielectric loss tangent
And (3) the following materials: 0.0012 or more
O: 0.0010 or more and less than 0.0012
Delta: 0.0080 or more and less than 0.0010
X: less than 0.0080 (including the same value and positive difference)
Dielectric constant
And (3) the following materials: 0.12 or more
O: 0.10 or more and less than 0.12
Delta: 0.08 or more and less than 0.10
X: less than 0.08 (including the same value and positive difference)
Evaluation criterion in examples 28 to 43 and comparative examples 19 to 40
Evaluation was performed by using the difference between the dielectric loss tangent and the dielectric constant of comparative example 19, which does not include a block copolymer, and that of each example or comparative example (comparative example 19-example or comparative example).
Dielectric loss tangent
And (3) the following materials: 0.010 or more
O: 0.008 or more and less than 0.010
Delta: 0.005 or more and less than 0.008
X: less than 0.005 (including the same value and positive difference)
Dielectric constant
And (3) the following materials: 0.4 or more
O: 0.3 or more and less than 0.4
Delta: 0.2 or more and less than 0.3
X: less than 0.2 (including the same value and positive difference)
Evaluation criterion in examples 44 to 55 and comparative examples 41 to 55
Evaluation was performed by using the difference between the dielectric loss tangent and the dielectric constant of comparative example 41 containing no block copolymer and that of each example or comparative example (comparative example 41-example or comparative example).
Dielectric loss tangent
And (3) the following materials: 0.0012 or more
O: 0.0010 or more and less than 0.0012
Delta: 0.0080 or more and less than 0.0010
X: less than 0.0080 (including the same value and positive difference)
Dielectric constant
And (3) the following materials: 0.15 or more
O: 0.12 or more and less than 0.15
Delta: 0.10 or more and less than 0.12
X: less than 0.10 (including the same value and positive difference)
(2) Strength (glass transition temperature: tg)
The dynamic viscoelasticity of the resin compositions of examples and comparative examples described later was measured, and the temperature at which tan δ was maximum was determined as the glass transition temperature (Tg).
A high Tg indicates high strength over a wide temperature range.
The measurement apparatus used ARES (trade name manufactured by TAInstruents Co.) was set in a stretching mode, and a test piece having a length of 35mm, a width of about 12.5mm and a thickness of 0.3mm was cut out from a cured film described later as a measurement sample.
The measurement was carried out at a frequency of 10rad/s and a measurement temperature of-150 to 270 ℃.
((3) storage stability)
The varnishes of examples and comparative examples described below were observed after standing at 30 ℃/50% rh, and the number of days and the presence or absence of the varnish until the occurrence of layer separation and/or the precipitation of gel-like components were evaluated according to the following criteria.
And (3) the following materials: over 120 days (including no precipitation)
O: over 90 days
Delta: for more than 30 days
X: less than 30 days
[ production of resin composition ]
Examples 1 to 27 and comparative examples 1 to 18
Using the above components, a resin composition was prepared by the following preparation method.
The composition ratios and physical properties are shown in tables 3 to 6 below.
First, each component was added to toluene (special grade product manufactured by Wako pure chemical industries, ltd.) and stirred to dissolve, thereby preparing a varnish having a concentration of 20 to 50 mass%.
The varnish was applied onto the release treated KAPTON film at a speed of 30 mm/sec, and then dried at 100 ℃ for 30 minutes under a nitrogen stream using a forced air dryer to obtain a film. The obtained film was subjected to a curing reaction at 200℃for 90 minutes under a nitrogen stream by a blast dryer to obtain a cured film.
The cured film was supplied to an evaluation sample.
As is clear from examples 1 to 27 and comparative examples 1 to 18, cured products of the resin compositions using the block copolymers of the present invention are excellent in balance of dielectric properties, strength and heat resistance.
From the above, it is clear that the cured product of the resin composition containing the block copolymer of the present invention is suitable for glass cloth applications and printed wiring board applications using a metal laminate.
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Examples 28 to 43 and comparative examples 19 to 40
The following components were used in addition to the above components, and a resin composition was prepared according to the following preparation method.
< component (II): radical initiator
Perbutyl P-90 (manufactured by Nipple Co., ltd.)
< component (III): polar resin ]
Bisphenol A type epoxy resin EXA-850CRP (DIC Co., ltd.)
Phenoxy resin YP-50S (manufactured by Nissan iron chemical Co., ltd.)
< component (IV): curing agent
1-benzyl-2-phenylimidazole (Tokyo chemical industry Co., ltd.)
Phenol-based curing agent KA-1163 (DIC Co., ltd.)
The composition ratios and physical properties are shown in tables 7 to 9 below.
First, the resultant mixture was added to toluene in addition to a phenol-based curing agent, and stirred to dissolve the mixture, thereby preparing a varnish having a concentration of 20 to 50% by mass.
When a phenol-based curing agent is used, a phenol-based curing agent solution having a concentration of 50% by mass is prepared using methyl ethyl ketone (a special grade product manufactured by Wako pure chemical industries, ltd.) as a solvent, and is added to a varnish containing components other than the phenol-based curing agent, followed by stirring to prepare a varnish.
The varnish was coated onto the release treated KAPTON film at a speed of 30 mm/sec, and then dried at 100 ℃ for 30 minutes using a forced air dryer under a nitrogen stream to obtain a film.
The obtained film was subjected to a curing reaction at 200℃for 90 minutes under a nitrogen stream by a blast dryer to obtain a cured film.
The cured film was supplied to an evaluation sample.
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Examples 44 to 55 and comparative examples 41 to 55
The following components were used in addition to the above components, and a resin composition was prepared according to the following preparation method.
< component (III): polar resin ]
[ polyimide resin ]
Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70) (manufactured by KI chemical Co., ltd.)
4,4' -bismaleimide diphenylmethane (BMI-H) (manufactured by KI chemical Co., ltd.)
< component (IV): curing agent
Cyanate ester curing agent 2, 2-bis (4-cyanate phenyl) propane (manufactured by tokyo chemical Co., ltd.)
Diamine curing agent 4,4' -diaminodiphenylmethane (manufactured by Tokyo chemical Co., ltd.)
The composition ratios and physical properties are shown in tables 10 and 11 below.
First, a polyimide resin as a polar resin and a cyanate curing agent and/or a diamine curing agent as a curing agent were dissolved at 160℃in the mixing ratio shown in tables 10 to 11 below, and reacted with stirring for 6 hours to obtain a bismaleimide-triazine resin oligomer.
The obtained bismaleimide triazine resin oligomer was dissolved in toluene, and the remaining components were added and stirred to dissolve, thereby preparing a varnish having a concentration of 20 to 50 mass%.
The above varnish was coated onto the release treated KAPTON film at a speed of 30 mm/sec. After that, the film was dried at 100℃for 30 minutes using a forced air dryer under a nitrogen stream.
The film was subjected to a maximum curing reaction of 90 minutes at 200℃under a nitrogen stream by means of a blast dryer to obtain a cured film.
The cured film was supplied to an evaluation sample.
From examples 28 to 55 and comparative examples 19 to 55, it is apparent that cured products of the resin compositions using the block copolymers of the present invention are excellent in balance of dielectric properties, strength and heat resistance.
From the above, it is clear that the cured product of the resin composition containing the block copolymer of the present invention is suitable for glass cloth applications and printed wiring board applications using a metal laminate.
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Industrial applicability
The block copolymer, the resin composition containing the block copolymer, and the cured product of the block copolymer of the present invention are industrially useful as materials for films, prepregs, electronic circuit boards, and next-generation communication boards.

Claims (12)

1. A block copolymer having:
a polymer block (A) mainly composed of vinyl aromatic monomer units; and
a polymer block (B) mainly composed of conjugated diene monomer units and/or a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units,
The block copolymer satisfies the following conditions (i) to (ii),
< condition (i) >
The weight average molecular weight of the block copolymer is 3.5 ten thousand or less;
< condition (ii) >
The content of the vinyl aromatic monomer unit in the block copolymer is 55 to 95 mass%.
2. The block copolymer of claim 1, which further satisfies the following condition (iii),
< condition (iii) >
The polymer block (B) and/or the polymer block (C) contains a unit (a) derived from 1, 2-bonding and/or 3, 4-bonding and a unit (B) derived from 1, 4-bonding, and the content of the unit (a) derived from 1, 2-bonding and/or 3, 4-bonding is 80% or less, with the total content of the polymer block (B) and/or the polymer block (C) set to 100%.
3. A resin composition comprising:
component (I): the block copolymer of claim 1 or 2; and
at least one component selected from the group consisting of the following components (II) to (IV),
component (II): a free radical initiator;
component (III): a polar resin excluding the component (I);
component (IV): curing agent, excluding component (II).
4. The resin composition according to claim 3, wherein the component (III) is at least one selected from the group consisting of an epoxy resin, a polyimide resin, a polyphenylene ether resin, a liquid crystal polyester resin and a fluorine resin.
5. A cured product comprising the block copolymer according to claim 1 or 2.
6. A cured product of the resin composition according to claim 3.
7. A resin film comprising the resin composition according to claim 3.
8. A prepreg which is a composite of a substrate and the resin composition according to claim 3.
9. The prepreg of claim 8 wherein the substrate is glass cloth.
10. A laminate comprising the resin film according to claim 7 and a metal foil.
11. A laminate comprising a cured product of the prepreg according to claim 8 and a metal foil.
12. A material for an electronic circuit board, comprising the cured product according to claim 6.
CN202310135115.0A 2022-03-04 2023-02-20 Block copolymer, resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit board Pending CN116693781A (en)

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