KR101948874B1 - Resin composition, manufacturing method the same, prepreg including the same, laminated plate including the same, metal foil coated with resin including the same - Google Patents

Abstract

The present invention relates to: a resin composition, a method for manufacturing the same, a prepreg comprising the same, a laminate comprising the same, and a resin-coated metal foil comprising the same. Specifically, embodiments of the present invention, in order to solve the above-mentioned problems, provide the resin composition having good coefficient of thermal expansion (CTE) and an adhesive force, while having low elasticity and low dielectric properties, thereby being processed in forms of a prepreg, a laminate sheet, a copper clad laminate and the like, and become suitable for application to electric devices such as automobiles.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition, a process for producing the same, a prepreg containing the same, a laminate including the same, and a metal foil with a resin containing the same. BACKGROUND ART INCLUDING THE SAME}

A resin composition, a process for producing the same, a prepreg containing the same, a laminate comprising the same, and a resin-coated metal foil containing the same.

Recently, as the demand for high-performance electronic devices is increasing, organic materials having various characteristics are attracting attention.

For example, organic materials used in electric devices such as automobiles are required not only low dielectric properties but also low elasticity, and also have a good thermal expansion coefficient (CTE) and adhesion.

Epoxy resin, Teflon resin, cyanate resin, and the like are known as organic materials to be applied to such electric devices. However, Teflon resin has a remarkably low adhesive property and cyanate resin is easily gelled, which limits its use.

As a result, an epoxy resin having relatively low dielectric properties and having high adhesion properties and being easy to use has been widely used. However, since a known epoxy resin contains a polar group, it has disadvantages in that it is disadvantageous in terms of signal propagation speed and impedance control in a high frequency region, and has limitations in fields requiring low elasticity.

In embodiments of the present invention, in order to solve the above-mentioned problems, it has a low coefficient of thermal expansion (CTE) and an adhesive strength while having low elasticity and low dielectric properties, and it has a form such as prepreg, laminated sheet, To provide a resin composition suitable for application to electric devices such as automobiles.

In this specification, when a part is referred to as " including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

In the present specification, the term " combination thereof " included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, ≪ / RTI > and the like.

As used herein, unless otherwise defined, at least one hydrogen in the compound is a C1 to C30 alkyl group; A C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C10 alkylsilyl group; A C3 to C30 cycloalkyl group; A C6 to C30 aryl group; A C1 to C30 heteroaryl group; A C1 to C10 alkoxy group; A silane group; Alkylsilane groups; An alkoxysilane group; An amine group; An alkylamine group; An arylamine group; An ethyleneoxy group or a halogen group.

As used herein, " hetero " means an atom selected from the group consisting of N, O, S and P, unless otherwise defined.

As used herein, unless otherwise defined, the term " alkyl group " means a " saturated alkyl group " which does not include any alkenyl group or alkynyl group; Or an " unsaturated alkyl group " comprising at least one alkenyl or alkynyl group. The term " alkenyl group " means a substituent having at least two carbon atoms constituting at least one carbon-carbon triple bond. it means. The alkyl group may be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C20 alkyl group, and specifically may be a C1 to C6 lower alkyl group, a C7 to C10 intermediate alkyl group, or a C11 to C20 higher alkyl group.

For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are present in the alkyl chain, which includes methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t- Indicating that they are selected from the group.

Typical examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, Pentyl group, cyclohexyl group, and the like.

&Quot; An aromatic group " means a substituent in which all the elements of the cyclic substituent have p-orbital, and these p-orbital forms a conjugation. Specific examples thereof include an aryl group and a heteroaryl group.

An " aryl group " includes a single ring or a fused ring, i.e., a plurality of ring substituents that divide adjacent pairs of carbon atoms.

&Quot; Heteroaryl group " means an aryl group containing a heteroatom selected from the group consisting of N, O, S and P in an aryl group. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

Unless otherwise defined herein, "copolymerization" may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and the term "copolymer" means a block copolymer, random copolymer, graft copolymer or alternating copolymer It can mean merging.

Based on the above definitions, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Resin composition

In one embodiment of the present invention, there is provided a resin composition comprising a first modified epoxy resin.

The resin composition of one embodiment can have a good coefficient of thermal expansion (CTE) and adhesion, while having the low elasticity and low dielectric constant, by including the first modified epoxy resin.

Further, in addition to the first modified epoxy resin, the resin composition of one embodiment may further include other materials (for example, a second modified epoxy resin, a reactive diluent, etc., described later) There is room for improvement.

The first modified epoxy resin, which is an essential constituent, will be described in detail below.

The first modified epoxy resin

Specifically, the first modified epoxy resin comprises a first polymer comprising the following repeating unit 1-1; And a second polymer having the following repeating unit 1-1, which is the same as or different from the first polymer, is connected by a linker represented by the following formula (1)

[Repeat unit 1-1]

In the repeating unit 1-1, R ₁ to R ₁₀ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, x1 may be a value that satisfies the range of 0 < x1 < 12, and more specifically, a value that satisfies the range of 0 &lt; x1 8.

[Chemical Formula 1]

In the above formula (1), * denotes a bonding site with the first polymer and the second polymer, respectively, and R ₁₂ to R ₂₁ each independently represent hydrogen; Or a substituted or unsubstituted C1 to C6 alkyl group. .

In the above formula (1), R ₁₁ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of the above substituents, a trimer formed by three of the three substituents, or a substituent having a structure in which they are mixed.

Specifically, R ₁₁ in the formula (1) may be derived from a polyisocyanate compound having an (O = C = N) nR ₁₁ structure. More specifically, R ₁₁ in the formula (1) may correspond to a residue other than an isocyanate group from a polyisocyanate compound having the structure (O = C = N) nR ₁₁ wherein n is an integer of 1 to 5 And may be specifically from 1.5 to 4, more specifically from 2 to 3).

For example, the polyisocyanate compound may be a polyisocyanate compound,

Methylenebis (cyclohexyl isocyanate));

(MDI) having more isocyanate groups than &quot; polymeric " (hereinafter referred to as " polyisocyanurate "), MDI having more isocyanate groups (Methylene diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI)) -based compound, which may be referred to as &quot; -MDI &quot;

A toluene diisocynate (TDI) -based compound including 2,4-toluene diisocynate and 2,6-toluene diisocynate;

m-xylylene diisocyanate;

Hexamethylene diisocyanate (HMDI); And

An isomer thereof, a derivative thereof, or a mixture of two or more thereof selected from the group consisting of isophorone diisocyanate (IPDI).

In the above-exemplified polyisocyanate compound, the residue other than the isocyanate group may be R ₁₁ of the above formula (1).

More specifically, for example, R ₁₁ in the above formula (1) may be selected from the group consisting of methylenebis (cyclohexyl), methylene diphenylene, methylphenylene, m- xylylene, hexamethylene and isophoronylene; an isomer thereof, a derivative thereof, or a mixture of two or more selected from the group consisting of xylylene, hexamethylene, and isophoronylene; Or more.

In other words, the first modified epoxy resin has 1) a structure in which the first polymer and the second polymer are bonded to each other, with the linker represented by Formula 1 being the center.

1) In the first modified epoxy resin, the linker represented by Formula 1 includes a urethane group.

Here, the urethane group may be formed by a combination of a substance having an isocyanate and a substance having a hydroxy group. Through the selection of these materials, soft segments and hard sengments of the urethane groups can be controlled and suitably controlled to realize low elastic properties of the final object.

Therefore, the first modified epoxy resin can exhibit low elasticity properties by having a structure centered on a linker represented by the above-mentioned formula (1).

2) In the first modified epoxy resin, the first polymer and the second polymer may have the same or different structures, but commonly include a structure represented by the repeating unit 1-1.

Here, the structure represented by the recurring unit 1-1 may refer to a structure based on an epoxy resin containing a DCPD (Dicyclopentadiene) structure, wherein the epoxy group is modified by a substituted or unsubstituted phenol. Here, when the epoxy group is modified by the substituted phenol, the substituent of the phenol is hydrogen; Or a C1 to C6 alkyl group.

In general, epoxy resins have relatively low dielectric properties, are known to have high adhesion properties, and are easy to use. The structure of DCPD is also known to be advantageous for exhibiting low dielectric properties. Epoxy resins It is known that the heat resistance is improved by the modification of

In this regard, the first modified epoxy resin can exhibit low dielectric properties, adhesiveness, and heat resistance by including the first polymer and the second polymer.

In short, the first modified epoxy resin has the following properties: 1) it exhibits low elasticity properties by including a linking group represented by the above-mentioned formula 1 at the center of its structure; and 2) based on two kinds of polymers bonded on both sides of such a linking group Low dielectric constant, adhesiveness, and heat resistance.

On the other hand, in the first modified epoxy resin, the first polymer and the second polymer may each independently include at least one repeating unit of the following repeating units 1-2 and 1-3, Not:

 [Repeat unit 1-2]

In the repeating unit 1-2, R ₂₂ to R ₂₆ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, x2 may be a value satisfying the range of 0 < x2 &amp;le; 12, and more specifically, a value satisfying the range of 0 &

[Repeat unit 1-3]

In the repeating units 1-3, R ₂₇ to R ₃₁ each independently may be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, x3 may be a value satisfying the range of 0 < x3 < = 12, specifically, a value satisfying the range of 0 &lt;

Regardless of whether the repeating unit 1-2 is contained or not, the first polymer and the second polymer may each independently have a C6 to C30 aryl group substituted or unsubstituted with an epoxy group as a terminal. Specifically, the first polymer and the second polymer may each independently have a terminal represented by the following formula.

In the above formulas, R ₃₂ to R ₃₆ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. In the above formula, the symbol * denotes a site to be bonded to the terminal of each of the first polymer and the second polymer.

On the other hand, the first modified epoxy resin may have a number average molecular weight of 1,500 to 3,500 and a weight average molecular weight of 3,500 to 4,500, but the resin composition of the embodiment is not limited thereto.

The second modified epoxy resin

As described above, in addition to the first modified epoxy resin, the resin composition of one embodiment may optionally include a second modified epoxy resin.

The second modified epoxy resin may be a copolymer comprising the following repeating units 2-1 and 2-2:

[Repeat unit 2-1]

[Repeat unit 2-2]

In the repeating unit 2-1, R ₁ to R ₁₀ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, y1 may be a value satisfying the range of 0 < y1 &amp;le; 12, specifically, a value satisfying a range of 0 &

In the repeating unit 2-2, R ₂₂ to R ₂₆ each independently may be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, y2 may be a value satisfying 0 <y2? 12, specifically 0 <y2? 8.

In the second modified epoxy resin, the repeating unit 2-1 is based on an epoxy resin containing a DCPD (Dicyclopentadiene) structure, similar to the repeating unit 1-1 of the first modified epoxy resin, May refer to a structure in which the epoxy group is modified by a phenol that is converted. Here, when the epoxy group is modified by the substituted phenol, the substituent of the phenol is hydrogen; Or a C1 to C6 alkyl group.

In the second modified epoxy resin, the repeating unit 2-2 may be a structure based on an epoxy resin containing a DCPD structure, and the epoxy group may not be denatured.

In this regard, the second modified epoxy resin includes the repeating units 2-1 and 2-2 to exhibit low dielectric properties, adhesiveness, and heat resistance.

The second modified epoxy resin may further include the following repeating unit 2-3, but is not limited thereto:

[Repeat unit 2-3]

In the repeating unit 2-3, R ₂₇ to R ₃₁ each independently may be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, y3 may be a value satisfying the range of 0 < y3 &amp;le; 12, and more specifically, a value satisfying the range of 0 &

The second modified epoxy resin may be a terminally substituted or unsubstituted C6 to C30 aryl group regardless of whether the repeating unit 2-3 is included or not. Specifically, the second modified epoxy resin may have a terminal represented by the following formula.

In the above formulas, R ₃₂ to R ₃₆ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. In the above formula, the symbol * denotes a site to be bonded to the terminal of the second modified epoxy resin.

On the other hand, when the composition of one embodiment further comprises the second modified epoxy resin, the epoxy equivalence range of the composition may be 230 to 950 g / eq, for example 250 to 650 g / eq. In this range, the low elasticity, low dielectric constant, high heat resistance, low CTE effect, and excellent workability can be exhibited, but the composition of this embodiment is not limited thereto.

Reactive diluent

The resin composition of one embodiment may further include a reactive diluent in addition to the first modified epoxy resin.

In this case, the resin composition of one embodiment may comprise a mixture of the first modified epoxy resin and a reactive diluent, or may comprise a mixture of the first modified epoxy resin, the second modified epoxy resin and a reactive diluent.

In the resin composition of one embodiment, as the reactive diluent, a reactive diluent generally used in the field of resin production can be used.

For example, the reactive diluent may include a compound represented by the following formula (2).

(2)

In the above formula (2), R ₃₇ may be represented by the following formula (2A) or (2B).

(2A)

(2B)

In Formula 2A, z is a value satisfying the range of 0 < z < = 20, and more specifically, may be a value satisfying the range of 0 &lt; In the formulas (2A) and (2B), an asterisk denotes a moiety connected to R ₃₇ in the formula (2).

Method for producing resin composition

In another embodiment of the present invention, there is provided a method for producing a resin composition comprising the aforementioned first modified epoxy resin.

The resin composition containing the above-mentioned first modified epoxy resin may be contained in the product obtained by continuously performing the two-step process.

Specifically, the manufacturing method of one embodiment may be one in which the first step and the second step described below are successively performed.

Step 1: A step of reacting a polymer represented by the following formula (3) and a compound represented by the following formula (4) in a reactor to obtain a first product

Step 2: A step of adding a polymer represented by the following formula (5) to the reactor in which the first step is completed and reacting with the first product to obtain a second product

(3)

In Formula 3, R ₃₈ to R ₄₇ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, 0 < m1 &amp;le; 12, and more specifically, 0 &lt;

[Chemical Formula 4]

(O = C = N) nR &lt; ₁₁ &gt;

In the formula (4), n may be 1 to 5, specifically 1.5 to 4, more specifically 2 to 3. R ₁₁ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of these substituents, a trimer formed by three of the three substituents, or a substituent having a structure in which the two are substituted, The above formula (1) can be referred to.

 [Chemical Formula 5]

In Formula 5, R ₄₈ to R ₆₂ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group. Here, 0 < m < = 12, and more specifically, 0 &lt;

Hereinafter, each step will be described in detail.

First step

In the first step, the polymer represented by Formula 3 is a DCPD (Dicyclopentadiene) polymer, and may be a substituted or unsubstituted phenol group. When the phenol group contained in the polymer represented by Formula 3 includes a substituent, the substituent may be hydrogen or a C1 to C6 alkyl group.

The compound represented by the formula (4) may be a polyisocyanate compound having a structure of (O = C = N) nR ₁₁ . From this, a structure of R _{11 in} the above-described formula (1) can be formed, and the description of R ₁₁ is redundant and thus omitted.

Accordingly, in the first step, when the reaction between the polymer represented by Formula 3 and the compound represented by Formula 4 proceeds, the compound represented by Formula 4 is converted into a linker, And the polymer represented by the general formula (3) are bonded to each other to form the reaction product.

Specifically, the reaction product of the polymer represented by the formula (3) and the compound represented by the formula (4) may be a polymer represented by the following formula (6).

[Chemical Formula 6]

In Formula 6, R ₆₃ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of these substituents, a trimer formed by three of the three substituents, or a substituent having a structure in which the two are substituted, May be the same as R < ₁₁ &gt; in the formula (1).
In the above formula (6), R ₆₄ to R ₈₃ are each independently hydrogen or a substituted or unsubstituted C 1 to C 6 alkyl group, n 1 is a value satisfying 0 <n 1 12, n 2 is 0 &lt; n2 12. For the explanation, R ₃₈ to R _{47 and m} 1 in the above formula (3) can be referred to.

In the urethane bond formation reaction, a tertiary amine catalyst such as bis (2-dimethylaminoethyl) ether, trimethylaminoethylethanolamine and N, N'-dimethylethanolamine, dibutyltin dilaurate, Such as dibutyl tin diacetate, etc., in an amount of 100 to 3,000 ppm on the basis of the formula (4), or the catalyst may be used at all, and the reaction may be carried out at a reaction temperature of 50 to 160 ° C for 30 minutes It is preferable to carry out the reaction for 6 hours.

However, when the first step is terminated, unreacted starting materials may remain. The first product according to the first step may include a reaction product of the polymer represented by Formula 3 and the compound represented by Formula 4; And a polymer represented by the above-mentioned general formula (3).

In the first step, the molar ratio of the hydroxyl group of the polymer represented by the formula (3) and the isocyanate group of the compound represented by the formula (4) may be controlled to be 66: 1 to 1.1: 1. In this range, as the number of isocyanate groups in the formula (4) increases, it is advantageous in low elasticity, but the risk of gelation in the polymerization degree and the workability due to the high viscosity But the present invention is not limited thereto.

The molar ratio of the hydroxyl group of the polymer represented by the formula (3) and the isocyanate group of the compound represented by the formula (4) can be controlled to be specifically 20: 1 to 1.5: 1, no.

On the other hand, the first step can be carried out either with the solvent or without the solvent. The solvent used herein may be any one selected from the group consisting of a ketone solvent, an acetate solvent, a carbitol solvent, an aromatic hydrocarbon solvent, and an amide solvent, or a mixture of two or more thereof.

Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the acetate solvent include ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, Examples of the toole-based solvent include cellosolve and butyl carbitol. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methylpyrrole Money.

Second Step

The second step is carried out by introducing the polymer represented by Chemical Formula 5 into the reactor in which the first step is completed, without taking measures such as purifying or separating the product (first product) of the first step .

The time point of introduction of the compound of formula (5) may be added at the beginning of the first step or may be introduced at the beginning of the second step or may be carried out by any method.

In the second step, the polymer represented by Formula 5 is a DCPD (Dicyclopentadiene) polymer containing an epoxy group.

Accordingly, in the second step, when the reaction of the polymer represented by the formula (6) and the polymer represented by the formula (5) proceeds in the first product, the reaction site is converted to the repeating unit 1-1 described above, The linker contained in the polymer represented by the formula (6) can be directly converted to the above-described formula (1) to form the above-mentioned first modified epoxy resin as a whole.

On the other hand, when the polymer represented by the general formula (3) remains in the first product, the polymer may also be reacted with the polymer represented by the general formula (5).

Specifically, when the reaction of the polymer represented by the formula (3) and the polymer represented by the formula (5) proceeds, the reaction site is converted into the repeating unit 2-1 described above and the polymer represented by the formula (5) The reactive site can be converted to the above-mentioned repeating unit 2-2 to form the above-mentioned second modified epoxy resin as a whole.

Of course, even when the second step is terminated, unreacted starting materials may remain.

On the other hand, when the hydroxyl group of the polymer represented by the formula (6) and the hydroxyl group of the unreacted polymer represented by the formula (3) of the first product are reacted with the epoxy group of the polymer represented by the formula (5) The epoxy group molar ratio can be controlled from 1: 30 to 1: 1.5. This may mean that the OH group moles: EPOXY moles = 1: 30 to 1: 1.5.

In this range, as the number of moles of hydroxyl group increases, it is considered that high heat resistance, low CTE and high adhesive strength are favorable, but there is a risk of gelation during polymerization and workability due to high molecular weight. However, no.

In the above-mentioned reaction, it is preferable to use at least one compound selected from the group consisting of 2-phenylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, Ethyl-5-methylimidazole), an amine-based catalyst, a phosphine-based catalyst such as tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, or a phosphonium salt catalyst, 3, preferably from 100 to 3,000 ppm, and the reaction is preferably carried out at a reaction temperature of 100 to 250 ° C for 1 to 10 hours. Accordingly, the product (second product) in the second step essentially contains the first modified epoxy resin, and the second modified epoxy resin, the unreacted raw materials (Chemical Formula 6 and 5) in the second step And may be optionally included.

Third step

And a third step of adding and mixing a reactive diluent into the reactor in which the second step is completed without taking measures such as refining or separating the product (second product) of the second step However, this is an optional process.

When the third step is further included, the reactive diluent may be added in an amount of 1 to 35 parts by weight based on 100 parts by weight of the total weight of the second product. In this range, various properties of low elasticity, heat resistance, and low CTE are properly balanced, but the manufacturing method of the embodiment is not limited thereto.

The structure and the like of the reactive diluent are the same as described above.

The prepreg

In another embodiment of the present invention, there is provided a prepreg comprising a fiber substrate, wherein the resin composition is impregnated in the fiber substrate.

For example, the prepreg of the embodiment can be produced by impregnating the fiber substrate with a varnish composition comprising the resin composition and the solvent as described above, followed by drying.

In the case of the above-mentioned fiber substrate, although not particularly limited, a fiber substrate such as a woven fabric or a nonwoven fabric can be used. For example, inorganic fibers such as glass, alumina, asbestos, boron, silica alumina glass, silica glass, chirano, silicon carbide, silicon nitride, and zirconia, aramid, polyetheretherketone, polyetherimide, polyethersulfone, Organic fibers such as cellulose, and mixed fiber based materials thereof may be used.

The solvent may be any one selected from the group consisting of a ketone solvent, an acetate solvent, a carbitol solvent, an aromatic hydrocarbon solvent, and an amide solvent, or a mixture of two or more thereof.

Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the acetate solvent include ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, Examples of the toole-based solvent include cellosolve and butyl carbitol. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methylpyrrole Money.

The impregnation conditions in the preparation of the prepreg in one embodiment are not particularly limited, but the solid content in the varnish composition can be adjusted in consideration of proper viscosity and workability when impregnating the fibrous substrate.

The drying conditions for the preparation of the prepreg in the above embodiment are not particularly limited, but the varnish composition may be heat-treated in a temperature range of 20 to 200 캜 for 1 to 30 minutes in a state impregnated with the fiber substrate , And it may be advantageous in the range of interlaminar adhesion of the laminate.

Laminates

According to another embodiment of the present invention, there is provided a laminate in which at least two layers of prepregs of the above-described embodiment are laminated.

For example, the laminate of this embodiment can be produced by laminating one or more prepregs of the above-described embodiment, and laminating a metal foil on one side or both sides thereof, if necessary, followed by heating and pressing.

In addition, the multi-stage press, multi-stage vacuum press, continuous molding, autoclave molding machine or the like may be used as the device for heating and pressing in the production of the laminate of the embodiment, but the laminate of the embodiment is not limited thereto.

In the case of using the metal foil in the production of the laminate of one embodiment, the metal foil is not particularly limited, but may be at least one metal selected from the group consisting of copper, aluminum, nickel, nickel-phosphorus, nickel-tin alloy, nickel- One or more sheets of metal foil may be used.

Metal foil with resin

In another embodiment of the present invention, there is provided a resin-coated metal foil comprising: a metal foil; and a resin layer comprising the resin composition of one embodiment described above.

For example, the resin-coated metal foil of the embodiment can be produced by preparing a resin composition which is not processed into a prepreg, as in the above-described embodiment, with a varnish composition, applying the composition to a metal foil and then drying the resin foil.

The varnish composition for producing the resin-coated metal foil of one embodiment may further include a solvent as well as a curing agent, a curing catalyst, and the like as the varnish composition for preparing the prepreg described above.

The curing agent may be one selected from the group consisting of phenol novolak resin, cresol novolak resin, dicyclopentadiene resin, and dicyandiamide, or a mixture of two or more thereof.

The curing catalyst may be any one selected from the group consisting of an imidazole compound, a phosphine compound, a phosphonium salt, and a tertiary amine, or a mixture of two or more thereof.

The resin composition of one embodiment can have a good thermal expansion coefficient (CTE) and an adhesive strength while having the low elasticity property and the low dielectric property by including the first modified epoxy resin.

This can be processed in the form of a prepreg, a laminated sheet, a copper clad laminate, or the like, and is suitable for being applied to an electric apparatus such as an automobile.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example 1

1) First step (step 1)

180 g of DCPD-phenol resin (product name: KDN-7011, OHEW 186 g / eq by Kukdo Chemical Co., SP 105 ° C) was charged into a four-necked flask equipped with a stirrer, a nitrogen inlet and a reflux tube connected to a cooling tube, &Lt; / RTI &gt; The DCPD-phenol resin is a solid raw material having m1 of 1 to 7, number average molecular weight of 565 and weight average molecular weight of 784 in the following general formula (3).

(3)

After the temperature in the four-necked flask was stabilized and the DCPD-phenol resin was completely melted, 0.1 ml of a 10 wt% dibutyltin dilaurate catalyst solution (in MEK) was added.

The temperature of the four-necked flask equipped with the catalyst was raised to 130 DEG C, and when the temperature was stabilized, the NCO content of MDI (4,4'-diphenylmethane diisocyanate, product name: COSMONATE PI, Kumho Mitsui Chemicals, 33.6 wt%) was added dropwise thereto.

After completion of the dropwise addition of the MDI, the mixture was stirred at 130 DEG C for 3 to 4 hours to carry out the reaction of the first step.

2) the second step (step 2)

1800 g of DCPD-epoxy resin (product name: KDCP-150, Kukdo Chemical Co., Ltd., EEW 287.5 g / eq, SP 79.7 占 폚) was added to the four-necked flask in which the second step was completed and then melted at 130 占 폚 . The DCPD-epoxy resin is a solid raw material having a number average molecular weight of 598 and a weight average molecular weight of 1,005 in the following formula (5).

[Chemical Formula 5]

After the temperature of the four-necked flask was stabilized and all of the DCPD-epoxy resin was melted, 0.1 ml of a catalyst solution (in MeOH) in which 10% by weight of 2-phenylimidazole was dissolved was added.

The temperature of the four-necked flask in which the catalyst was charged was raised to 160 ° C, and the reaction was allowed to proceed in the second step with stirring for 3 to 4 hours while the temperature was stabilized.

3) Third step (step 3)

874 g of methyl ethyl ketone (MEK) as a solvent was added to the four-necked flask in which the second step was completed, and the reaction product of the second step was diluted.

As a result of the analysis of the finally obtained resin composition, it was confirmed that the epoxy equivalent was 357.1 g / eq and the viscosity was 5,237 cps (@ 25 DEG C).

Example 2

1) & 2) The first step (step 1) and the second step (step 2)

The same procedure was applied to the second step of Example 1.

3) Third step (step 3)

300 g of Trimethylol Propane triglycidyl ether (trade name: YH-300, manufactured by Kukdo Chemical Co., Ltd., EEW 138.5 g / eq, viscosity 115 cps) was added to a four-necked flask, 25 ° C) was charged, and 1002 g of the same MEK as in Example 1 was added to dilute the reaction product of the second step. The trifunctional reactive diluent to liquid wonryoyi being, to be displayed in the formula (2) as is the formula 2B R _37, to the formula 2B * display represented by the formula (2) refers to the region that is connected to R ₃₇ of formula (II) do.

(2)

(2B)

As a result, the resin composition finally obtained was found to have a number average molecular weight of 689, a weight average molecular weight of 2092, an epoxy equivalent of 294.8 g / eq, and a viscosity of 1,745 cps (@ 25 DEG C).

Example 3

1) First step (step 1)

Except for using HDI (hexamethylene diisocyanate, Asahi Kasei Co., Ltd., NCO content of 50 wt% per mole of HDI) instead of MDI. The remainder was the same as the first step of Example 1.

2) Second step

In the four-necked flask in which the first step of Example 3 was completed, the second step was carried out by using the same raw materials, conditions, and the like as in the second step of Example 1. [

3) Third step

300 g of a bifunctional reactive diluent (Aliphatic glycidyl ether (trade name: PG-207P, Kukdo Chemical Co., Ltd., EEW 318.3 g / eq, viscosity 47 cps at 25 ° C) was added to a four- The reaction product of the second step was diluted by adding 1002 g of the same solvent (MEK) as in Example 1 after the dropwise addition. The bifunctional reactive diluent is a liquid raw material represented by the following formula (2-1), R ₃₇ in the following formula (2-1) is represented by the following formula (2A), and z in the following formula (2A) is specifically 0 to 11, Means a moiety connected to R ₃₇ of the following formula (2-1).

[Formula 2-1]

(2A)

As a result, the final resin composition was found to have a number average molecular weight of 3,141, a weight average molecular weight of 13,880, an epoxy equivalent of 366 g / eq, and a viscosity of 676 cps (@ 25 DEG C).

Comparative Example 1

(Trade name: KDP-555MC80, available from Kukdo Chemical Co., Ltd., EEW 225.4 g / eq, viscosity: 16,600 cps at 25 DEG C) was used as a heat-resistant high-heat resistant DOPO-HQ modified phosphorus epoxy resin.

Comparative Example 2

A commercially available DCPD-epoxy resin (trade name: KDCP-130EK80, Kukdo Chemical Co., Ltd., EEW 254.7 g / eq, viscosity 1,150 cps at 25 ° C) was used.

Comparative Example 3

A commercially available phenol novolac epoxy resin (trade name: YDPN-638EK80, Kido Chemical Co., Ltd., EEW 179.7 g / eq, viscosity 370 cps at 25 ° C) was used.

Evaluation example 1

The physical properties of each of the examples and comparative examples were evaluated in the following manner, and the evaluation results thereof were recorded in the following Table 1.

(1) Evaluation method

1) Method of preparing sample for CCL evaluation

As the curing agent, phenol novolac curing agent having a softening point of 91.2 ° C was used, 2MI (2Methylimidazole) was used as a catalyst and M2 EPO was used as a filler. Each of the examples and comparative examples, the curing agent, , And a varnish solution having a solid content of 50% by weight was prepared by using MEK as a solvent.

Each varnish solution was impregnated with 2116 type E-glass glass fiber and then placed in an oven at 175 DEG C for 2 minutes to prepare each prepreg.

Each of the prepregs was placed between two copper foils of 1 oz., Hot pressed at a temperature of 180 ° C. and a pressure of 200 psi for 1 hour and 30 minutes, .

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 CCL
Evaluation Piece
Furtherance
(unit:
Weight part) Epoxy resin
(Epoxy Resin) 58 56 58 51 53 48 Hardener PN ^{* 1} 12 14 12 19 17 22 Catalyst 0.08 Filler 30 Properties
evaluation
result Tg (占 폚, DSC) 161 125 117 177 180 170 CTE (ppm / ° C) X 12 12 12 15 15 16 Y 12 13 12 15 16 17 Z 45 34 47 45 45 47 Storage Modulus (GPa) 1.0 0.8 0.6 2.0 2.1 1.9 Dk (@ 1 GHz) 3.9 3.9 3.9 4.3 4.0 4.5 Df (@ 1 GHz) 0.011 0.012 0.011 0.015 0.015 0.019 Td (占 폚) 420.3 420.1 420.1 372 423 394 90 [deg.] Peel Strength (kgf / mm ² ) 1.2 1.2 1.2 1.1 0.9 0.8

2) Glass transition temperature (Tg)

The glass transition temperature (Tg) was measured by keeping the resin composition of each of the examples and comparative examples at 180 DEG C for 6 hours and then by using differential scanning calorimetry (DSC) according to the IPC TM-650 2.4.25 standard .

3) Coefficients of thermal expansion (CTE)

The coefficient of thermal expansion (CTE) of the resin compositions of each of the examples and comparative examples was maintained at 180 캜 for 6 hours and cured, and then measured according to the IPC TM-650 2.4.24 standard.

4) Storage modulus

The storage elastic modulus was obtained by attaching the resin composition of each of the Examples and Comparative Examples to a metal foil to prepare a metal foil with each resin adhered thereto, Respectively. Each of the double-sided copper-clad laminated foils was entirely etched, cut into 5 mm wide and 30 mm long, and calculated by DMA (Dynamic Mechanical Analysis).

5) Dielectric Properties

IPC TM-650 2.5.5.9 The dielectric constant (Dk) and dielectric dissipation factor (Df) at 1 GHz were measured for the CCL specimens of the examples and comparative examples according to the standard.

6) Decomposition Temperatures (Td)

The thermal decomposition temperature (Td) was determined by keeping the resin composition of each of the examples and the comparative examples at 180 캜 for 6 hours and curing the resin composition according to the IPC TM-650 2.4.24.6 standard using a thermal analysis method (TGA).

7) Peel Strength

According to the IPC TM-650 2.4.8 standard, the 90 ° peel strength was measured for the CCL specimens of each of the examples and comparative examples.

(2) Review of evaluation result

That is, each of the embodiments has a low modulus characteristic and a low dielectric property, and has a good coefficient of thermal expansion (CTE) and adhesion, as compared with the respective comparative examples. This is because the prepreg, laminated sheet, And can be evaluated by a thermosetting resin composition suitable for application to electric devices such as automobiles.

1) Evaluation of storage elasticity

Specifically, according to Table 1, it can be seen that each embodiment exhibits a storage modulus in comparison with each comparative example, and thus has a characteristic of suppressing solder crack with high reliability .

Unlike the comparative examples, the reason why the low storage modulus is shown in each of the examples is that the urethane bond is introduced and the reactive diluent is added.

As described above, the urethane bond can be formed by bonding a substance having an isocyanate and a substance having a hydroxy group. Through the selection of these materials, soft segments and hard sengments of the urethane groups can be controlled and suitably controlled to realize low elastic properties of the final object.

 In this regard, the difference between Examples 2 and 3 lies in the fact that, based on the difference in isocyanate material used in each example, the structure formed between the urethane bonds is somewhat different. In the case of Example 2 in which a urethane bond is formed using 4,4'-diphenylmethane diisocyanate (MDI), it can be seen that a benzene ring exists between the urethane bonds. On the other hand, in Example 3 in which urethane bonds are formed using hexamethylene diisocyanate (HDI), an aliphatic ring exists between urethane bonds. As such, depending on the structure formed between the urethane bonds, the low elasticity properties may be partially different. This is also the reason why the low elastic effect is more advantageous in Example 3 than in Example 2.

On the other hand, by introducing a reactive diluent, low elasticity and low viscosity can be realized, and as a result, workability can be improved while lowering the modulus. In this connection, the difference between Examples 1 and 3 can be found also in the kind of reactive diluent.

More specifically, in the case of Example 1 in which a reactive diluent is not used, the storage elastic modulus is 1.0 GPa. In the case of Example 2 in which trimethylolpropane triglycidyl ether was used as a reactive diluent in an amount of 13% of the total composition (excluding solvent) . It can be confirmed that the storage elastic modulus is realized to be 0.8 GPa. Also, in the case of Example 3 using Aliphatic glycidyl ether as the reactive diluent in an amount of 13%, it can be confirmed that the storage elastic modulus is realized to be 0.6 GPa. As described above, the effects of Examples 1 to 3 can also be dependent on the kind and presence or absence of the reactive diluent.

2) Evaluation of dielectric properties

On the other hand, from the evaluation results of the dielectric constant (Dk) and the dielectric loss factor (Df) in Table 1, it can be seen that each of the Examples shows low dielectric properties and decreases the dielectric loss ratio in comparison with the respective Comparative Examples.

It can be deduced that the dielectric constant was lowered by the effect of introducing the DCPD structure of the formula (5) used in the first step of each example and the second step used in the second step.

Specifically, the DCPD structure is bulky, rigid, and non-polar, yet has a symmetrical structure. Due to these structural characteristics, DCPD can be advantageous for realizing low dielectric properties. Compared to the DCPD structure epoxy of the formula (5) and the comparative example (2) used in the second step of each example, the dielectric material of the material thus synthesized is superior in dielectric properties. This is because the composition to be synthesized has a DCPD structure and the formation rate of the secondary alcohol group after the curing of the epoxy group is reduced as the epoxy group of the varnish composition is reduced by the first process.

Claims (22)

A first polymer comprising the following repeating unit 1-1; And a second polymer which is the same as or different from the first polymer, the first polymer comprising a first modified epoxy resin and a second polymer,
Resin composition:
[Repeat unit 1-1]

In the repeating unit 1-1,
R ₁ to R ₁₀ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
x1 is a value satisfying the range of 0 < x1 &lt; 12,
[Chemical Formula 1]

In Formula 1,
R ₁₁ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of the above substituents, a trimer formed by three of these substituents, or a substituent having a structure in which they are mixed,
* Indicates a bonding site of the first polymer and the second polymer, respectively,
R ₁₂ to R ₂₁ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group.
The method according to claim 1,
Wherein the first polymer and the second polymer are each, independently,
And further comprises the following repeating units 1-2.
Resin composition:
[Repeat unit 1-2]

In the repeating unit 1-2,
R ₂₂ to R ₂₆ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
x2 is a value satisfying the range of 0 < x2? 12.
The method according to claim 1,
Wherein the first polymer and the second polymer are each, independently,
And further comprises the following repeating units 1-3.
Resin composition:
[Repeat unit 1-3]

In the repeating units 1-3, R ₂₇ to R ₃₁ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group, and x3 is a value satisfying 0 <x3? 12.
The method according to claim 1,
Wherein the first polymer and the second polymer each independently have a C6 to C30 aryl group substituted or unsubstituted with an epoxy group.
Resin composition.
5. The method of claim 4,
Wherein the first polymer and the second polymer each independently comprise a terminal represented by the following formula:
Resin composition:

In the above formulas, R ₃₂ to R ₃₆ may each independently be hydrogen or a substituted or unsubstituted C1 to C6 alkyl group;
* Indicates a site to be bonded to the ends of the first polymer and the second polymer, respectively.
The method according to claim 1,
And a second modified epoxy resin, which is a copolymer comprising the following repeating units 2-1 and 2-2.
Resin composition:
[Repeat unit 2-1]

[Repeat unit 2-2]

In the repeating unit 2-1,
R ₁ to R ₁₀ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
y1 is a value satisfying the range 0 <y1? 12,
In the repeating unit 2-2,
R ₂₂ to R ₂₆ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
y2 is a value satisfying the range of 0 < y2? 12.
The method according to claim 6,
The second modified epoxy resin may contain,
And further comprises the following repeating units 2-3.
Resin composition:
[Repeat unit 2-3]

In the repeating unit 2-3,
R ₂₇ to R ₃₁ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group, and y3 is a value satisfying 0 <y3? 12.
The method according to claim 6,
The epoxy equivalent weight of the resin composition is 230 to 950 g / eq.
The method according to claim 1,
&Lt; / RTI &gt; further comprising a reactive diluent.
Resin composition.
10. The method of claim 9,
The reactive diluent may include,
Wherein R < 1 &gt;
Resin composition.
(2)

In Formula 2,
R ₃₇ is represented by the following formula (2A) or (2B)
(2A)

(2B)

In the formula (2A), z is a value satisfying a range of 0 &lt;
In each of the formulas (2A) and (2B), an asterisk denotes a site connected to R ₃₇ in the formula (2).
A first step of reacting a polymer represented by the following formula (3) and a compound represented by the following formula (4) in a reactor to obtain a first product; And
And a second step of adding a polymer represented by the following formula (5) to the reactor in which the first step is terminated and reacting with the first product to obtain a second product:
Method of producing resin composition:
(3)

In Formula 3,
R ₃₈ to R ₄₇ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
m1 is a value satisfying 0 < m1 12
[Chemical Formula 4]
(O = C = N) nR < ₁₁ &gt;
In Formula 4,
n is from 1 to 5,
R ₁₁ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of the above substituents, a trimer formed by three of these substituents, or a substituent having a structure in which they are mixed,
[Chemical Formula 5]

In Formula 5,
R ₄₈ to R ₆₂ are each independently hydrogen or a substituted or unsubstituted C 1 to C 6 alkyl group
m2 is a value satisfying 0 &lt; m &lt;
12. The method of claim 11,
Wherein the ratio of the number of moles of hydroxyl groups of formula (3) to the number of moles of isocyanate groups of formula (4) is from 66: 1 to 1.1: 1.
12. The method of claim 11,
Wherein the first product comprises:
A reaction product of the polymer represented by Formula 3 and the compound represented by Formula 4; And
And a polymer represented by the general formula (3).
A method for producing a resin composition.
14. The method of claim 13,
The reaction product of the polymer represented by the formula (3) and the compound represented by the formula (4)
Is a polymer represented by the following formula (6)
Method of producing resin composition:
[Chemical Formula 6]

In Formula 6,
R ₆₃ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of the above substituents, a trimer formed by three of these substituents, or a substituent having a structure in which they are mixed,
R ₆₄ to R ₈₃ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group;
n1 is a value satisfying 0 < n1 12, and n2 is a value satisfying 0 < n2 12.
15. The method of claim 14,
Wherein the second product comprises:
A reaction product of the polymer represented by Formula 5 and the polymer represented by Formula 6;
A reaction product of the polymer represented by Formula 3 and the polymer represented by Formula 5; And
And a polymer represented by the general formula (5)
A method for producing a resin composition.
16. The method of claim 15,
The reaction product of the polymer represented by the formula (5) and the polymer represented by the formula (6)
A first polymer comprising the following repeating unit 1-1; And a second polymer which is the same as or different from the first polymer, the second polymer being a first modified epoxy resin, the second polymer being connected by a linker represented by the following formula (1)
Method of producing resin composition:
[Repeat unit 1-1]

In the repeating unit 1-1, R ₁ to R ₁₀ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
x1 is a value satisfying the range of 0 < x1 &lt; 12,
[Chemical Formula 1]

In Formula 1,
R ₁₁ is a C 2 to C 30 alkylene group substituted or unsubstituted with a C 1 to C 3 alkyl group; A C3 to C30 cycloalkylene group substituted or unsubstituted with a C1 to C3 alkyl group; A C3 to C30 cycloalkenylene group substituted or unsubstituted with a C1 to C3 alkyl group; And a C6 to C30 arylene group substituted or unsubstituted with a C1 to C3 alkyl group; , A dimer formed by two of the above substituents, a trimer formed by three of these substituents, or a substituent having a structure in which they are mixed,
* Indicates a bonding site of the first polymer and the second polymer, respectively,
R ₁₂ to R ₂₁ are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group.
12. The method of claim 11,
And a third step of adding and mixing a reactive diluent into the reactor in which the second step is terminated.
A method for producing a resin composition.
18. The method of claim 17,
The reactive diluent may include,
And 1 to 35 parts by weight based on 100 parts by weight of the total weight of the second product.
A method for producing a resin composition.
Fiber substrates; And
The resin composition according to any one of claims 1 to 10 impregnated into the fiber substrate.
Prepreg.
The laminate according to claim 19, wherein at least two prepregs are laminated.
21. The method of claim 20,
Wherein the laminated plate comprises:
Wherein the prepreg is heated and pressed in a state in which at least two or more layers of the prepreg are laminated,
Laminates.
Metal foil; And
A resin layer disposed on the metal foil and comprising the resin composition according to any one of claims 1 to 10;
Metal foil with resin.