KR101920205B1 - Manufacturing method of hardener for preparing cured product having low dielectric constant - Google Patents

Abstract

The present invention relates to a curing agent, a composition for use in the preparation thereof, and a method for producing a curing agent using the same, more specifically, to a resin composition comprising a specific polymer capable of providing a resin product having low dielectric properties and high heat resistance A composition for use in the preparation thereof, and a process for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a curing agent for the production of a low dielectric constant and high heat resistant cured product for an epoxy resin,

TECHNICAL FIELD The present invention relates to a curing agent composition, a curing agent having low dielectric constant and high heat resistance, and a method for producing the same.

As the amount of information of an electronic device using a printed circuit board becomes wider, electronic products are also speeded up and densified, the circuit line width is reduced, and a large amount of heat is generated when a high-speed signal is transmitted by mounting components larger than a unit area.

Such heat may cause problems such as deformation of the substrate due to the difference in CTE between the parts and the material. In addition, since the use of Pb is totally prohibited due to environmental regulations such as RoHS, the soldering temperature is increased by 20 ° C to 40 ° C Therefore, materials such as lead free high Tg and high heat resistance are required.

Also, the current speed of personal computers is over 2 GHz in 1 GHz, and in the high frequency range in mobile phones. The higher the frequency, the more problems that can occur in signal transmission. Lowering the dielectric constant of the material by reducing the overall transmission speed and noise can also reduce noise.

Generally, a method of increasing the heat resistance of an epoxy resin can be realized by increasing the cross-linking density between the epoxy resin and the curing agent. When the novolak-based curing agent is used, the heat resistance of the cured product itself can be increased. However, Due to the characteristics, dielectric constant and dielectric loss, which are electrical characteristics, are increased. It is known that the effect of alcoholic OH generated in the curing reaction of epoxy resin is great. Moisture is promoted by the high free volume due to the hydrogen bonding between alcoholic OH and moisture and the network structure of epoxy itself .

Generally, the heat resistance can be increased by using a multifunctional novolac curing agent or epoxy for improving the heat resistance. However, due to the high moisture absorption characteristics and the high free volume, dielectric constant and dielectric loss can be increased Lt; / RTI >

In addition, there is a method of lowering the dielectric constant and the dielectric constant by using a styrene maleic-anhydride (SMA) resin as a curing agent as a method for enhancing the electrical characteristics. However, the SMA resin has a disadvantage in that the curing density with the epoxy is remarkably reduced and the heat resistance and adhesion property are deteriorated.

Korean National Publication No. 10-2015-0079446 (published on July 27, 2015)

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an epoxy resin composition which can realize a high glass transition temperature by having an epoxy resin and a high curing density, To provide a curing agent for use in the production of a cured product. That is, it is an object of the present invention to provide a low dielectric constant and high heat resistant curing agent, a composition for use in the preparation thereof, and a method for producing the low dielectric constant and high heat resistant curing agent using the same.

The present invention provides a curing agent composition for the production of a cured product having a low dielectric constant and a high heat resistance, which comprises a styrene compound represented by the following formula (1), an anhydride compound represented by the following formula (2) A mixed monomer containing an acrylic compound to be displayed; A polymerization initiator; And a solvent.

[Chemical Formula 1]

R ¹ in the general formula (1) is a hydrogen atom or an alkyl group having ¹ to 3 carbon atoms, and R ² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

(2)

R ³ and R ⁴ in the general formula (2) are independently a hydrogen atom or a C1-C5 alkyl group.

(3)

R ⁵ in the formula (3) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁶ is a hydrogen atom, a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, R ⁷ is a hydrogen atom, a C 1 to C 5 alkyl group, a cyclic alkyl group of C8, phenyl group or - a (CH _{2) m} OH, in this case, m is a natural number of 1-5.

In one preferred embodiment of the present invention, the composition of the present invention may comprise 4 to 12 parts by weight of the polymerization initiator and 180 to 300 parts by weight of the solvent, based on 100 parts by weight of the monomer.

In one preferred embodiment of the present invention, the monomer may include the styrene compound, the anhydride compound, and the acrylic compound in a molar ratio of 1: 0.15 to 0.40: 0.03 to 0.28.

In one preferred embodiment of the present invention, the acrylic compound may include an acrylic compound represented by the following Formula 3-1 and an acrylic compound represented by the following 3-2 in a molar ratio of 1: 0.5-1.

[Formula 3-1]

R ⁵ to R ⁷ in the general formula (3-1) are all hydrogen atoms.

[Formula 3-2]

R ⁵ is a hydrogen atom, R ⁶ is a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, R ⁷ is a C 2 to C 3 alkyl group, a C 5 to C 8 cyclic alkyl group, a phenyl group, or - (CH ₂ ) _m OH, wherein m is a natural number of 1 to 5.

In one preferred embodiment of the present invention, the solvent in the composition of the present invention is an alcohol-based solvent containing at least one selected from 1-butanol, 2-butanol, isopropyl alcohol and methanol; And a ketone-based solvent containing at least one selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone, and acetone.

In one preferred embodiment of the present invention, the solvent may include an alcohol solvent and a ketone solvent at a weight ratio of 2 to 4: 1.

In a preferred embodiment of the present invention, the polymerization initiator is selected from the group consisting of benzoyl peroxide (BPO), t-butyl peroxide, dicumyl peroxide and azobisisobutylonitrile (AIBN; Azobisisobutyronitrile). ≪ / RTI >

Another object of the present invention is to provide a method for producing a curing agent for the production of a cured product of low dielectric constant and high heat resistance using the above composition, wherein the styrene compound represented by the formula (1) and the acrylic compound represented by the formula And raising the temperature to a reflux temperature of 115 ° C to 125 ° C to prepare a first mixture; A second step of dropping a second mixture of an anhydride-based compound, a polymerization initiator, and a ketone-based solvent represented by the formula (2) into the mixture to prepare a third mixture; Performing a reflux and a polymerization reaction on the third mixture; And a fourth step of performing a dehydration and extraction process on the third mixture subjected to the polymerization reaction to obtain a polymer represented by the following general formula (4).

[Chemical Formula 4]

Wherein R ¹ is a hydrogen atom or an alkyl group having ¹ to 3 carbon atoms, R ² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to ³ carbon atoms, R ³ and R ⁴ are independently a hydrogen atom or a C 1 to C 5 and the alkyl group, R ⁵ is a hydrogen atom or an alkyl group C1 ~ C3, R ⁶ is a hydrogen atom, an alkoxy group of C1 ~ C5 alkyl group or a C1 ~ C5 a, R ⁷ is a hydrogen atom, an alkyl group, C5 of C1 ~ C5 ~ C8 cyclic alkyl group, a phenyl group or - a (CH _{2) m} OH, wherein, m is 1-5 natural numbers x, y and z is from 1: 0.15 ~ 0.40 0.03 ~ 0.28 the molar ratio is, n is the weight of the compound Average molecular weight of 8,000 to 30,000.

In one preferred embodiment of the present invention, the reflux and the polymerization in three stages can be carried out at 110 to 125 ° C.

The low dielectric constant and high heat resistant curing agent of the present invention thus prepared may have an acid value of 120 to 225 mg KOH / g.

Still another object of the present invention relates to a prepreg comprising a cured product using the above-mentioned curing agent, and it includes a cured product of varnish including an epoxy resin, the aforementioned curing agent and an accelerator.

In one preferred embodiment of the present invention, the cured product may have a glass transition temperature (Tg) of 180 ° C to 250 ° C.

As a preferred embodiment of the present invention, the cured product has a dielectric constant and dielectric loss measurement (thickness) of 0.8 to 1 mm using an impedance analyzer (Agilent E4991B) at a measurement frequency of 1 GHz and a measurement temperature of 25 to 27 ° C , The dielectric constant (D _k ) is 3.35 or less, and the dielectric loss (Df) is 0.02 or less.

In one preferred embodiment of the present invention, the epoxy resin may be a phenol novolac-based epoxy resin.

The curing agent of the present invention is excellent in bonding force with an epoxy resin to ensure a high curing density of the epoxy resin, and it is possible to secure heat resistance by improving the thermal property of a product manufactured using an epoxy resin, By securing the characteristics, the electrical characteristics of the product can be improved. Therefore, the curing agent of the present invention is suitable for use as a curing agent for a resin used for manufacturing products such as a CCL (Copper Clad laminate), a sealing agent for electronic parts, and an adhesive, which are required to have low dielectric constant and high heat resistance.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a composition for use in the production of a curing agent for the production of a cured product of low dielectric constant and high heat resistance, which comprises a styrene compound represented by the following formula (1), an anhydride compound represented by the following formula A mixed monomer comprising a compound; A polymerization initiator; And a solvent.

[Chemical Formula 1]

R ¹ in the general formula (1) is a hydrogen atom or an alkyl group having ¹ to 3 carbon atoms, preferably a hydrogen atom or a methyl group. R ² in the formula (1) is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group or a C1 to C2 alkoxy group, more preferably a hydrogen atom or a methyl group .

(2)

R ³ and R ⁴ in the general formula (2) are independently a hydrogen atom or a C 1 to C 5 alkyl group, preferably a hydrogen atom or a C 1 to C 2 alkyl group.

(3)

R ⁵ in the general formula (3) is a hydrogen atom or a C1-C3 alkyl group, preferably a hydrogen atom or a C1-C3 alkyl group. R ⁶ in the general formula (3) is a hydrogen atom, a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, preferably a hydrogen atom or a C 1 to C 2 alkyl group. In formula (3), R ⁷ is a hydrogen atom, a C 1 to C 5 alkyl group, a C 5 to C 8 cyclic alkyl group, a phenyl group, or - (CH ₂ ) _m OH wherein m is a natural number of 1 to 5, (CH ₂ ) _m OH wherein m is a natural number of 1 to 3, more preferably a hydrogen atom, a C 1 to C 2 alkyl group, Alkyl group or - (CH ₂ ) _m OH, wherein m is a natural number of 1 to 3.

In the composition of the present invention, the mixed monomer may contain the styrene compound, the anhydride compound, and the acrylic compound in a molar ratio of 1: 0.15 to 0.40: 0.03 to 0.28, preferably 1: 0.18 to 0.38 : 0.05 to 0.25 molar ratio. If the molar ratio of the unhydride compound is less than 0.15 with respect to 1 mole of the styrene compound, there may be a problem that the bonding property with the epoxy is poor and the heat resistance is lowered. If the molar ratio of the anhydride compound is 0.40 There is a problem that the content of styrene becomes relatively low to increase the dielectric constant and the dielectric loss, and the reactivity is high, so that the molecular weight increases sharply during the synthesis, so that the resin may be hardened. If the molar ratio of the acrylic compound is less than 0.03 mol based on 1 mol of the styrene compound, the glass transition temperature of the curing agent may be too low. If the molar ratio exceeds 0.28 mol, the heat resistance of the cured product prepared using the curing agent of the present invention The glass transition temperature is improved, but the dielectric constant and the dielectric loss are increased and the electrical characteristics may be reduced.

In the composition of the present invention, the acrylic compound may be an acrylic compound represented by the formula (3), preferably an acrylic compound represented by the following formula (3-1) and an acrylic compound represented by the following formula (3-2) 1 molar ratio may be advantageous in terms of improvement of heat resistance and improvement of electrical characteristics.

[Formula 3-1]

R ⁵ to R ⁷ in the general formula (3-1) are all hydrogen atoms.

[Formula 3-2]

R ⁵ in the formula (3-2) is a hydrogen atom, R ⁶ is a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, preferably R ⁶ is a hydrogen atom or a C 1 to C 2 alkyl group. And, R ⁷ is of the formula 3-2 cyclic alkyl group, a phenyl group of C2 ~ C3 alkyl group, a C5 ~ C8 of and - (CH _{2) m} OH, and, wherein, m is natural number of 1-5, preferably R ⁷ It is an alkyl group or a hydrogen atom, C1 ~ C2 - and (CH _{2) m} OH, wherein, m is natural number of 1-3.

In the composition of the present invention, the polymerization initiator may be a conventional one used in the art, preferably, benzoyl peroxide (BPO), t-butyl peroxide, dicumyl peroxide ) And azobisisobutyronitrile (AIBN) may be used alone or in admixture of two or more. The amount of the polymerization initiator to be used may be 4 to 12 parts by weight, preferably 6 to 12 parts by weight, more preferably 6 to 10 parts by weight, based on 100 parts by weight of the mixed monomer. If the amount of the polymerization initiator used is less than 4 parts by weight, the polymerization time may become too long. If the amount of the polymerization initiator is more than 12 parts by weight, the reaction may proceed too quickly, and the weight average molecular weight of the curing agent represented by the following formula , There may be a problem that the synthesis yield of the curing agent is lowered.

Next, in the composition of the present invention, the solvent is a solvent capable of easily dissolving a mixed monomer, and may be a solvent commonly known in the art. Preferably, the solvent is 1-butanol, Alcohol-based solvents containing at least one selected from isopropyl alcohol and methanol; And a ketone solvent containing at least one selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone and acetone, and more preferably, the alcohol solvent and the ketone solvent are mixed at a ratio of 2 to 4: 1 by weight. The solvent may be used in an amount of 200 to 350 parts by weight, preferably 230 to 320 parts by weight, more preferably 250 to 300 parts by weight, based on 100 parts by weight of the mixed monomer. If the amount of the solvent is less than 200 parts by weight, the mixed monomer may not be sufficiently dissolved. If the amount of the solvent is more than 350 parts by weight, the polymerization reaction rate of the mixed monomers may be slowed down and the yield of the polymer may be lowered. It is good.

More specifically, the styrene compound represented by the formula (1) and the acrylic compound represented by the formula (3) are dissolved in an alcohol-based solvent And raising the temperature to a reflux temperature of 115 ° C to 125 ° C to prepare a first mixture; A second step of dropping a second mixture of an anhydride-based compound, a polymerization initiator, and a ketone-based solvent represented by the formula (2) into the mixture to prepare a third mixture; Performing a reflux and a polymerization reaction on the third mixture; And a fourth step of performing a dehydration and extraction process on the third mixture subjected to the polymerization reaction to obtain a polymer represented by the following formula (4).

 [Chemical Formula 4]

R ¹ in formula (4) is a hydrogen atom or an alkyl group having ¹ to 3 carbon atoms, preferably a hydrogen atom or a methyl group. R ² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group or a C1 to C2 alkoxy group, more preferably a hydrogen atom or a methyl group. R ³ and R ⁴ in the general formula (4) are independently a hydrogen atom or a C 1 to C 5 alkyl group, preferably a hydrogen atom or a C 1 to C 2 alkyl group. R ⁵ in the general formula (4) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁶ in the general formula (4) is a hydrogen atom, a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, preferably a hydrogen atom or a C 1 to C 2 alkyl group. R ⁷ in the general formula (4) is a hydrogen atom, a C 1 to C 5 alkyl group, a C 5 to C 8 cyclic alkyl group, a phenyl group, and - (CH ₂ ) _m OH wherein m is a natural number of 1 to 5. Preferably, R ⁷ is a hydrogen atom, a straight-chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or - (CH ₂ ) _m OH, wherein m is a natural number of 1 to 5. More preferably a hydrogen atom, an alkyl group or a C1 ~ C2 - and (CH _{2) m} OH, wherein, m is natural number of 1-3.

X, y and z in the formula (4) are 1: 0.15-0.40: 0.03-0.28 molar ratio, preferably x, y and z are 1: 0.18-0.38: 0.05-0.25 molar ratio. The n in formula (4) is a rational number satisfying the weight average molecular weight of the compound of 8,000 to 30,000, preferably 9,000 to 27,000, and more preferably 10,000 to 25,500.

In the method for producing a curing agent for producing a low dielectric constant and high heat resistant cured product according to the present invention, the amount of the styrene compound and the acrylic compound in the first mixture in the first step and the amount of the unhydride compound and the polymerization initiator in the two- The same as described above. The content ratio of the first stage alcoholic solvent and the second stage ketone solvent in the total solvent and the amount of the solvent used are the same as described above.

The refluxing and polymerization in three stages can be carried out at 110 to 125 ° C, preferably at 110 to 115 ° C. When the temperature is less than 110 ° C, the polymerization reaction rate is too slow, , The polymerization reaction rate is fast but the yield of the polymer represented by the formula (4) may be lowered, and the weight average molecular weight of the polymer may be too high. Therefore, the polymerization reaction is preferably carried out at a temperature within the above range.

The composition of the present invention and the curing agent of the present invention prepared from this composition have an acid value of 120 to 225 mg KOH / g, preferably an acid value of 125 to 215 mg KOH / g, more preferably 130 to 210 mg KOH / g.

The prepreg including the cured product prepared using the curing agent may have low dielectric constant and high heat resistance. In a preferred embodiment, the prepreg containing the cured product is an epoxy resin, A cured product of a varnish comprising the curing agent and the accelerator of the invention. At this time, the epoxy resin may preferably be a phenol novolac-based epoxy resin.

The cured product has a glass transition temperature (Tg) of 180 ° C to 250 ° C, preferably 182 ° C to 240 ° C, and is excellent in heat resistance.

Further, the dielectric constant (D _k ) of the cured product is measured at a measurement frequency of 1 GHz and a measurement temperature of 25 ° C to 27 ° C using an impedance analyzer (Agilent E4991B) ) Of 3.35 or less and a dielectric loss (Df) of 0.02 or less, preferably having a dielectric constant (D _k ) of 2.75 to 3.32 and a dielectric loss (Df) of 0.0100 to 0.0200.

Therefore, it is possible to provide a prepreg for use in the production of various products requiring high heat resistance and low dielectric constant such as a printed circuit board (CCL), a sealing agent for electronic parts, and an adhesive using the above-mentioned curing agent.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[Example]

Example  One

In a kettle equipped with a thermometer, a cooling tube and a stirrer, 416.6 g (4 mol) of the styrene compound represented by the following formula 1-1, 14.41 g (0.2 mol) of the acrylic compound represented by the following formula 3-3, (1-butanol) were charged, and then the mixture was heated to a reflux temperature of about 118 ° C to prepare a first mixture.

Next, when the reflux is started, 98.06 g (1 mol) of the unhydride compound represented by the following formula (2-1), 294.18 g of methyl isobutyl ketone (MIBK) as a solvent, 42.33 g of peroxide (BPO) was added dropwise constantly over 3 hours using a dropping funnel.

After the dropwise addition was completed for 3 hours, reflux and polymerization were carried out at 113 ° C to 115 ° C for additional 3 hours. Then, dehydration and extraction were carried out at 200 ° C to obtain 520 g of a copolymer represented by the following general formula (4).

[Formula 1-1]

R ¹ and R ² in formula (1-1) are hydrogen atoms.

[Formula 2-1]

R ³ and R ⁴ in formula (2-1) are hydrogen atoms.

[Formula 3-3]

R ⁵ in Formula 3-3 is a hydrogen atom, R ⁶ is an alkyl group of C1, and R ⁷ is a hydrogen atom.

[Formula 4-1]

In Formula 4-1, R ¹ and R ² , R ³ , R ⁴ , R ⁵ and R ⁷ are each a hydrogen atom, R ⁶ is a C1 alkyl group, x = 1, y = 0.24 to 0.26, 0.06, and n is a rational number satisfying the weight average molecular weight of the compound of 10,948.

Example  2

416.6 g (4 mol) of the styrene compound of Example 1, 36.03 g (0.5 mol) of the acrylic compound of Example 1 and 905.26 g of 1-butanol were fed into a kettle equipped with a thermometer, a cooling tube and a stirrer, And the temperature was raised to 118 DEG C to prepare a first mixture.

Next, when the reflux was started, 98.06 g (1 mol) of the anhydride-based compound of Example 1, 294.18 g of MIBK and 44.06 g of BPO at a concentration of 75% were added to the first mixture over 3 hours using a dropping funnel . After completion of dropwise addition for 3 hours, reflux and polymerization were carried out for further 3 hours at 113 ° C to 115 ° C, followed by dehydration at 200 ° C and extraction to obtain 550 g of a copolymer.

Example  3

416.6 g (4 mol) of the styrene compound of Example 1, 50.44 g (0.7 mol) of the acrylic compound of Example 1 and 934.08 g of 1-butanol were introduced into a kettle equipped with a thermometer, a cooling tube and a stirrer, And the temperature was raised to 118 DEG C to prepare a first mixture.

Next, when the reflux started, 98.06 g (1 mol) of the unhydride compound of Example 1, 294.18 g of MIBK and 45.21 g of 75% BPO were added to the first mixture over a period of 3 hours . After completion of the dropwise addition for 3 hours, reflux and polymerization were carried out for 3 hours at 113 ° C to 115 ° C, followed by dehydration at 200 ° C to obtain 560g of a copolymer.

Example  4

416.6 g (4 mol) of the styrene compound of Example 1, 72.06 g (1.0 mol) of the acrylic compound of Example 1 and 977.32 g of 1-butanol were introduced into a kettle equipped with a thermometer, a cooling tube and a stirrer, And the temperature was raised to 118 DEG C to prepare a first mixture.

Next, when the reflux was started, 98.06 g (1 mol) of the unhydride compound of Example 1, 294.18 g of MIBK, and 46.94 g of 75% BPO were added to the first mixture over a period of 3 hours using a dropping funnel . After completion of the dropwise addition for 3 hours, reflux and polymerization were carried out for 3 hours at 113 ° C to 115 ° C, followed by dehydration at 200 ° C to obtain 580g of a copolymer.

Example  5

416.6 g (4 mol) of the styrene compound of Example 1, 36.03 g (0.5 mol) of the acrylic compound of Example 1 and 905.26 g of 1-butanol were fed into a kettle equipped with a thermometer, a cooling tube and a stirrer, And the temperature was raised to 118 DEG C to prepare a first mixture.

 Next, when the reflux started, 78.45 g (0.8 mol) of the unhydride compound of Example 1, 235.34 g of MIBK and 44.81 g of 75% BPO were added to the first mixture over 3 hours using a dropping funnel Were added dropwise constantly. After completion of dropwise addition for 3 hours, reflux and polymerization were carried out for 3 hours at 113 ° C to 115 ° C, followed by dehydration at 200 ° C and extraction to obtain 530 g of a copolymer.

Example  6

416.6 g (4 mol) of the styrene compound of Example 1, 39.04 g (0.3 mol) of the acrylic compound represented by the following formula 3-4 and 911.28 g of 1-butanol were added to a kettle equipped with a thermometer, a cooling tube and a stirrer The temperature was raised to a reflux temperature of about 118 캜 to prepare a first mixture.

 Next, when the reflux was started, 98.06 g (1 mol) of the unhydride compound of Example 1, 294.18 g of MIBK and 44.30 g of 75% BPO were added to the first mixture over a period of 3 hours using a dropping funnel . After completion of the dropwise addition for 3 hours, the mixture was refluxed and polymerized for further 3 hours at 113 ° C to 115 ° C. Then, dehydration at 200 ° C was carried out to obtain 550g of a copolymer represented by the following formula 4-2.

[Chemical Formula 3-4]

R ⁵ in Formula 3-4 is a hydrogen atom, R ⁶ is an alkyl group of Cl, and R ⁷ is -CH ₂ CH ₂ OH.

[Formula 4-2]

Wherein R ¹ and R ² , R ³ , R ⁴ and R ^{5 are} hydrogen atoms, R ⁶ is a C1 alkyl group, R ⁷ is -CH ₂ CH ₂ OH, x = 1, y = 0.24 To 0.26 and z = 0.074 to 0.076, and n is a rational number satisfying the weight average molecular weight of the compound of 17,130.

Example  7

416.6 g (4 mol) of the styrene compound of Example 1, 65.07 g (0.5 mol) of the acrylic compound of Example 6 and 963.34 g of 1-butanol were fed into a kettle equipped with a thermometer, a cooling tube and a stirrer, Lt; 0 > C to prepare a first mixture.

Next, when the reflux was started, 98.06 g (1 mol) of the unhydride compound of Example 1, 294.18 g of MIBK and 46.38 g of 75% BPO were added to the first mixture over 3 hours using a dropping funnel . After completion of dropwise addition for 3 hours, reflux and polymerization were carried out for 3 hours at 113 ° C to 115 ° C, followed by dehydration at 200 ° C and extraction to obtain 570 g of a copolymer.

Example  8

The acrylic compound was used in a molar ratio of 1: 0.7 in terms of the compound represented by the following formula (3-1) and the formula (3-2) instead of the acrylic compound represented by the formula (3-3) A copolymer was prepared in the same manner as in Example 1.

Comparative Example  One

416.6 g (4 mol) of the styrene compound of Example 1 and 833.2 g of 1-butanol were charged into a kettle equipped with a thermometer, a cooling tube and a stirrer, and then heated to a reflux temperature of about 118 캜 to prepare a first mixture.

Next, when the reflux started, 98.06 g (1 mol) of the unhydride compound of Example 1, 294.18 g of MIBK and 41.17 g of BPO at a concentration of 75% were added to the first mixture over a period of 3 hours using a dropping funnel . After completion of the dropwise addition for 3 hours, reflux and polymerization were carried out for 3 hours at 113 ° C to 115 ° C, followed by dehydration at 200 ° C and extraction to obtain 510 g of a copolymer.

Comparative Example  2

560 g of a copolymer was obtained using the same styrene compound, 1-butanol, anhydride compound, MIBK, and BPO as in Comparative Example 1, but using the composition ratios shown in Table 2 below.

Comparative Example  3 ~ Comparative Example  4

Using the same styrenic compound, 1-butanol, unhydral compound, MIBK and BPO as in Example 3, except that the molar ratios of the mixed monomers were varied as shown in Table 2 below, , A copolymer was obtained.

Comparative Example  5

Using the same styrenic compound, 1-butanol, unhydral compound, MIBK and BPO as in Example 3, except that the molar ratios of the mixed monomers were varied as shown in Table 2 below, , A copolymer was obtained.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Styrene-based
compound
(Unit g, A) (1-1) 416.6 416.6 416.6 416.6 416.6 416.6 416.6 Anhydride-based compound
(Unit g, B) 1-2 98.06 98.06 98.06 98.06 78.75 98.06 98.06 Acrylic compound
(Unit g, C) 3-3 14.41 36.03 50.44 72.06 36.03 - - 3-4 - - - - - 39.04 65.07 Mixed monomer mole ratio
(A: B: C) 1: 0.25:
0.05 1: 0.25:
0.125 1: 0.25:
0.175 1: 0.25:
0.25 1: 0.2:
0.125 1: 0.25:
0.075 1: 0.25:
0.125 Mixed monomer
(Parts by weight) 100 100 100 100 100 100 100 Polymerization initiator
(Parts by weight) BPO 8 8 8 8 8.44 8 8 solvent
(Parts by weight) 1-butanol 218.5 217.8 217.4 216.7 214.6 217.7 216.9 MIBK 55.6 53.4 52.1 50.1 44.3 53.1 50.7

division Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Styrene-based
compound
(Unit g, A) (1-1) 416.6 416.6 416.6 416.6 416.6 416.6 Anhydride-based compound
(Unit g, B) 1-2 98.06 147.09 147.09 39.22 176.51 98.06 Acrylic compound
(Unit g, C) 3-3 Total 14.45 g
(Formula 3-1: Formula 3-2 = 1: 0.7 molar ratio) - - 50.44 50.44 86.47 3-4 - - - - - Mixed monomer mole ratio
(A: B: C) 1: 0.25:
0.05 1: 0.25:
0 1: 0.375:
0 1: 0.1:
0.175 1: 0.45:
0.175 1: 0.25:
0.30 Mixed monomer
(Parts by weight) 100 100 100 100 100 100 Polymerization initiator
(Parts by weight) BPO 8 8 8 8 8 8 solvent
(Parts by weight) 1-butanol 218.5 219 226.1 218.5 218.5 218.5 MIBK 55.6 57.2 78.3 55.6 55.6 55.6

Experimental Example  One: Acid value  And molecular weight measurement

remind The weight average molecular weight and acid value of the copolymer (curing agent) obtained through Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

(1) Measurement of weight average molecular weight (Mw)

The polymer to be measured by GPC (gel permeation chromatography) was dissolved in tetrahydrofuran (THF) so as to have a concentration of 20,000 ppm, and the solution was injected into a GPC through a 40 μl autosampler. The mobile phase of GPC was loaded at a flow rate of 0.8 ml / min using tetrahydrofuran (THF) and the assay was carried out at 40 < 0 > C. The column was connected in series with three Waters HR-05, 4E, 5E. The detector was measured at 40 ° C using an RI detector.

(2) Acid value ( mgKOH / g)

An acetone solution was added to an amount of 0.1 g of the copolymer (curing agent) obtained in Examples and Comparative Examples to dissolve the copolymer sufficiently, and the acid value was determined by titration with NaOH using a phenolphthalein indicator and reversing with H ₂ SO ₄ solution.

Analysis item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Mw 10,948 11,641 14,368 24,098 14,873 17,130 23,409 Acid value 149 167 182 201 131 164 177 Analysis item Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 * Mw 15,489 15,339 22,345 8,480 38,462 22,966 * Acid value 191 67 112 140 221 198 *

Manufacturing example  1 to 8 and Comparative Manufacturing Example  1 to 5: Prepreg  Produce

10 g of phenol novolac epoxy resin (YUDEN-CHEMICAL, YDPN-638), 21.83 g of each of the curing agents prepared in Examples 1 to 7 and Comparative Examples 1 and 2, and 0.036 g of 2-Mehtyl imidazole as an accelerator, Respectively.

Next, each varnish was cured using an oven. The curing conditions were pre-cured at 50 DEG C for 6 hours and then cured at 90 DEG C for 1 hour, at 120 DEG C for 1 hour, and at 150 DEG C for 2 hours to obtain a prepreg Examples 1 to 7 and Comparative Production Examples 1 and 2 were respectively performed.

Experimental Example  2 : Of prepreg (hardened)  Property measurement

The glass transition temperature and dielectric constant of the prepregs prepared in the Preparation Examples and Comparative Preparations were measured by the following methods, and the results are shown in Tables 5 to 6 below.

(One) Tg (Glass Transition Temperature Measurement)

Prepreg specimens of Production Examples and Comparative Production Examples were measured by differential scanning calorimetry (DSC).

(2) Measurement of dielectric constant

The dielectric constant and dielectric tangent of the cured product were measured using an impedance analyzer (Agilent E4991B) for the prepreg specimens of the production examples and comparative production examples, and the results are shown in Table 3 below.

(Measurement frequency: 1 GHz, measurement temperature: 25 to 27 占 폚, measurement sample thickness: 0.9 mm)

Analysis item Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Tg (占 폚) 188 201 212 235 182 198 230 Dk (dielectric constant) 2.87 2.92 3.05 3.31 3.15 3.03 3.24 Df (dielectric loss) 0.0112 0.0135 0.0141 0.0170 0.0144 0.0157 0.0176 Analysis item Production Example 8 Comparative Preparation Example 1 Comparative Production Example 2 Comparative Production Example 3 Comparative Production Example 4 Comparative Preparation Example 5 * Tg (占 폚) 218 158 166 174 245 230 * Dk (dielectric constant) 3.04 2.89 3.01 3.14 4.04 4.18 * Df (dielectric loss) 0.0139 0.0131 0.0138 0.0146 0.0179 0.0181 *

The results of the tests of Table 4 are as follows: Comparative Preparation Example 1 and Comparative Preparation Example 2 using Comparative Example 1 and Comparative Example 2, which are curing agents prepared without using an acrylic compound, Comparative Example 2 prepared by using an anhydride at a mole ratio of 0.15 In Comparative Production Example 3 using the curing agent of Example 3, there was a problem that the Tg was as low as 175 占 폚 or less. In Comparative Preparation Example 4 in which the curing agent of Comparative Example 4 was prepared by using an anhydride in an amount exceeding 0.40 molar, there was a problem that the heat resistance was excellent but the dielectric constant and the dielectric loss were too high. It is believed to be associated with a high weight average molecular weight.

Also, the cured product of Comparative Preparation Example 5 in which the curing agent of Comparative Example 5, which had an acrylic compound in an amount exceeding 0.28 molar ratio, was introduced also had a problem that the dielectric constant and the dielectric loss were too high.

On the other hand, Examples 1 to 8 have a dielectric constant (D _k ) of 3.35 or less and a dielectric loss (Df) of 0.02 or less while having a high glass transition temperature of 180 ° C or more. .

Through the above Examples and Experimental Examples, the present invention can be used as a curing agent for resins used in the production of products such as CCL (Copper Clad laminate), sealing agent for electronic parts, and adhesive, which are required to have low dielectric constant and high heat resistance .

Claims (7)

delete delete delete delete delete A step for preparing a first mixture by adding a styrene compound represented by the following general formula (1) and an acrylic compound represented by the following general formula (3) to an alcoholic solvent and stirring the mixture at a temperature of 115 to 125 캜;
A second step of dropping a second mixture of an anhydride-based compound represented by the following formula (2), a polymerization initiator, and a ketone-based solvent into the first mixture to prepare a third mixture;
The third mixture is refluxed and the polymerization reaction is carried out at 113 to 125 캜; And
And a fourth step of performing a dehydration and extraction step of the third mixture subjected to the polymerization reaction to obtain a polymer represented by the following formula (4)
The third mixture in the second stage contains the styrene compound, the anhydride compound and the acrylic compound in a molar ratio of 1: 0.18 to 0.38: 0.05 to 0.25,
The ketone solvent in the two-stage process and the alcoholic solvent in the first process step are contained at a weight ratio of 1: 2 to 4,
Wherein the alcoholic solvent includes at least one selected from 1-butanol, 2-butanol, isopropyl alcohol and methanol, and the ketone solvent is at least one selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone and acetone / RTI >
6 to 12 parts by weight of the polymerization initiator and 230 to 320 parts by weight of the solvent are used relative to 100 parts by weight of the total weight of the styrene compound, the anhydride compound and the acrylic compound,
Wherein the polymer has an acid value of 130 to 210 mg KOH / g; and a method for producing a curing agent for the production of a low dielectric constant and high heat resistant cured product.
[Chemical Formula 1]

R ¹ in the general formula (1) is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a C 1 to C 2 alkoxy group,
(2)

R ³ and R ⁴ in the general formula (2) are independently a hydrogen atom or a C 1 to C 2 alkyl group,
(3)

R ⁵ in the formula (3) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ⁶ is a hydrogen atom or a C1 to C 2 alkyl group; R ⁷ is a hydrogen atom, a C 1 to C 3 alkyl group, a C 3 to C 5 branched alkyl group, (CH ₂ ) _m OH, wherein m is a natural number of 1 to 3,
[Chemical Formula 4]

R ¹ of formula (IV) is a hydrogen atom or a methyl group, R ² is an alkoxy group of a hydrogen atom, a methyl group, or C1 ~ C2, R ³ and R ⁴ are independently a hydrogen atom or an alkyl group C1 ~ C2, R ⁵ is hydrogen R ⁶ is a hydrogen atom or a C1 to C 2 alkyl group; R ⁷ is a hydrogen atom, a C 1 to C 3 alkyl group, a C 3 to C 5 branched alkyl group, or - (CH ₂ ) _m OH; , Wherein m is a natural number of 1 to 3, x, y and z are 1: 0.18 to 0.38: 0.05 to 0.25 molar ratio, and n is a rational number satisfying a weight average molecular weight of the compound of 10,000 to 25,500. delete