KR101960478B1 - Thermosetting resin composition and cured product of the same - Google Patents

Abstract

In embodiments of the present invention, in order to solve above-mentioned problems, an epoxy resin is hybridized with an inorganic element and an acid anhydride is glycol-modified, thereby realizing the same as a thermosetting resin composition. By obtaining a cured product from the composition, it is possible to be used as a suitable material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermosetting resin composition,

A thermosetting resin composition and a cured product thereof.

In recent years, in the field of electronic devices, there is an increasing demand for a material that exhibits excellent mechanical properties while possessing optical characteristics, and further, can have various morphological characteristics.

For example, there is a demand for a material capable of being realized in a curved shape, a flexible characteristic, and / or a bendable characteristic while having a high visible light transmittance before and after exposure to ultraviolet rays.

In order to meet such demands, a thermosetting resin composition containing an epoxy resin has been studied, but epoxy resins known in general are easily yellowish due to exposure to ultraviolet rays. Therefore, before exposure to ultraviolet rays, The visible light transmittance often decreases.

Furthermore, an acid anhydride curing agent generally compounded with an epoxy resin has a low mechanical property of the thermosetting resin, and the thermosetting resin has resistance to bending, warping, and the like, and is an obstacle to realizing various morphological characteristics do.

In embodiments of the present invention, in order to solve the above-mentioned problems, an epoxy resin is hybridized with an inorganic element, and the acid anhydride is modified with Glycol-modified to be realized as a thermosetting resin composition, A cured product is obtained from the composition and used as a suitable material.

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.

Thermosetting resin composition

In one embodiment of the present invention, there is provided a thermosetting resin composition comprising 1) a subject comprising a silicon-hybrid epoxy resin, and 2) a curing agent comprising a glycol-modified acid anhydride .

1) In general, it is known that an epoxy resin-based composition exhibits excellent visible light transmittance after thermal curing and is realized as a material having a transparent appearance. However, since the epoxy resin is susceptible to structural changes due to heat or ultraviolet rays, a cured product prepared from a composition based on an epoxy resin is easily yellowish due to exposure to ultraviolet rays, and the visible light transmittance is often lowered .

To solve this problem, in one embodiment, a subject including a silicon hybrid (Si-hybrid) epoxy resin was applied. Specifically, a part of the epoxy functional group in the epoxy resin is substituted with silicon (Si) to obtain a silicone hybrid (Si-hybrid) epoxy resin, which is applied as a subject of the composition.

By replacing a part of the epoxy functional groups in the epoxy resin with silicon (Si), the optical characteristics described above can be stabilized in the structure while maintaining the chemical / mechanical properties of the epoxy resin. Accordingly, the composition using the subject matter including the silicone hybrid (Si-hybrid) epoxy resin exhibits excellent visible light transmittance before and after exposure to ultraviolet rays, and can be realized as a material having a transparent appearance.

2) On the other hand, an acid anhydride curing agent, which is generally blended with an epoxy resin, causes the thermosetting resin to be easily broken by an external impact, and is resistant to changes in shape such as bending and warping. Accordingly, it has been pointed out that the acid anhydride curing agent is an inhibiting factor in improving the mechanical properties of the cured product or realizing various forms.

To solve this problem, in one embodiment, a curing agent comprising a glycol-modified acid anhydride was applied. Specifically, a part or all of the carboxylic acid anhydride functional group in the acid anhydride is reacted with a Glycol functional group to obtain a glycol-modified acid anhydride and applied as a curing agent for the composition.

As described above, when a carboxylic acid anhydride functional group in an acid anhydride is partially or completely reacted with a glycol functional group, the cured product can exhibit excellent mechanical properties without changing the curing function by heat. Furthermore, the cured product can be reduced in resistance to bending, twisting, and the like to be realized in various forms.

Accordingly, the composition according to one embodiment can exhibit excellent mechanical properties while having optical characteristics, and can be realized with a material having various morphological characteristics.

The composition according to one embodiment will be described in more detail as follows.

subject

As will be described later, the subject matter may be a product obtained by thermal polymerization of these raw materials using an epoxy resin and a silicone compound as raw materials.

Specifically, when heat is applied to a mixture containing an epoxy resin comprising a compound represented by the following formula (1) and a silicone compound represented by the following formula (2), the structure represented by the formula (1) Si-hybrid resin (A2) in which end, interior, or all epoxy groups are substituted with silicon (Si) can be produced.

[Chemical Formula 1]

In Formula 1, n is a number of 0 or more and 0.85 or less.

(2)

In Formula 2, R is the same or different from each other and is a substituted or unsubstituted C1 to C6 alkyl; or. Substituted or unsubstituted phenyl;

Specifically, the epoxy resin containing the compound represented by Formula 1 contains 98% by weight or more of a compound having n = 0 in Formula 1, and n is 1 or more, relative to the total amount (100% It may be refined to include it in its entirety. (The purification method will be described later.) Herein, the compound represented by the general formula (1) wherein n = 0 can be represented by the following general formula (1-1).

[Formula 1-1]

On the other hand, the thermal polymerization reaction product of the epoxy resin containing the compound represented by the formula (1) and the silicone compound represented by the formula (2) can not be thermally polymerized, and the epoxy resin having the structure represented by the formula The resin (A1) remains, and other unavoidable impurities may remain thereon.

In other words, the thermopolymerization product of the epoxy resin containing the compound represented by the formula (1) and the silicone compound represented by the formula (2) comprises an epoxy resin (A1); And a silicone hybrid (Si-hybrid) epoxy resin (A2) in which part or all of the epoxy functional groups in the epoxy resin (A1) are substituted with silicon (Si) .

In connection with the thermal polymerization reaction of the epoxy resin comprising the compound represented by the formula (1) and the silicone compound represented by the formula (2), the epoxy resin (A1) . Specifically, the epoxy resin (A1) contains 98% by weight or more of a compound having n = 0 in the formula (1) (i.e., a compound represented by the formula (1-1)) relative to the total amount (100% , and n is 1 or more.

In the above-mentioned subject matter, the silicon hybrid (Si-hybrid) epoxy resin (A2) is one in which part or all of the epoxy functional groups in the epoxy resin represented by the formula (1) are substituted with silicon (Si) May be a thermal polymer of the compound represented by the formula (1) and the silicone compound represented by the formula (2).

On the other hand, in the thermal polymerization reaction of the epoxy resin containing the compound represented by the formula (1) and the silicone compound represented by the formula (2), the silicon hybridization rate (or substitution rate) can be controlled to 10 to 80%. When the above-mentioned reaction product is used as the above-mentioned subject, 10 to 80% by weight of the silicon-hybrid epoxy resin (A2) is contained relative to the total amount (100% The remainder may include the above-mentioned epoxy resin (A1) and other unavoidable impurities.

Hardener

In the case of the above-mentioned curing agent, it may be a product obtained by thermal polymerization of these raw materials, using an acid anhydride and a glycol compound as raw materials.

Specifically, an acid anhydride comprising a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2); And a glycol compound represented by the following general formula (4), heat is applied to the mixture to form a structure represented by the general formulas (3-1) and (3-2) Glycol-modified acid anhydride (B2) in which a carboxylic acid anhydride functional group is modified by reacting with a glycol functional group can be produced.

[Formula 3-1]

[Formula 3-2]

[Chemical Formula 4]

In the formula (4), n is a number of 9 to 230. The glycol compound satisfying this requirement is one kind of polyethylene glycol (PEG) and may have a weight average molecular weight of 400 to 10,000 g / mol.

On the other hand, an acid anhydride including a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2); And the glycol-based compound represented by the following formula (4), the thermal polymerization reaction product of the compound represented by the following formula (3-1) and the compound represented by the following formula The anhydride (B1) remains, and other unavoidable impurities may remain thereon.

In other words, an acid anhydride containing a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2); And the glycol-based compound represented by the following formula (4) include acid anhydrides (B1); And a glycol-modified acid anhydride (B2) in which a part of the carboxylic acid anhydride functional group in the acid anhydride (B1) is substituted with a glycol functional group. It can be applied as a hardener.

Mixing of base and hardener

In one embodiment, the subject and the curing agent may be blended in an amount of 75 parts by weight or more and 110 parts by weight or less, based on 100 parts by weight of the subject. As described above, the cured product thermally cured from the composition thus compounded exhibits excellent visible light transmittance both before and after ultraviolet ray exposure, and can be realized with a material having a transparent appearance.

Specific physical properties evaluation methods will be described later. However, if the composition of the subject and the curing agent is specifically controlled within the above range, the cured product can realize various properties.

For example, when the curing agent is blended in an amount of more than 75 parts by weight, but less than 90 parts by weight, or more than 95 parts by weight, based on 100 parts by weight of the subject, So that it can be realized by a material which is less damaged by an external impact.

In particular, if the curing agent is blended in an amount of more than 75 parts by weight and less than 90 parts by weight based on 100 parts by weight of the subject, even if the cured product is changed by external force, the changed shape is returned to the original state by heat It can be realized as a material which can control the magnetic restoration characteristic by heat.

The thermosetting resin composition may further include a dilution solvent, a thermosetting catalyst, or a mixture thereof, which are generally known in the art, and a detailed description thereof will be omitted.

Method for producing thermosetting resin composition

In another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: applying heat to a mixture comprising an epoxy resin and a silicone compound to prepare a subject comprising a silicon-hybrid epoxy resin; A method for producing a thermosetting resin composition, comprising the steps of: applying heat to a mixture to prepare a curing agent containing a glycol-modified acid anhydride; and mixing the subject and the curing agent to obtain a thermosetting resin composition ≪ / RTI >

Each manufacturing process of the base and curing agent

Preparing a subject comprising the silicone hybrid (Si-hybrid) epoxy resin, and producing a curing agent comprising the glycol-modified acid anhydride, wherein the raw material, the process, and the product Is omitted as it is as described above.

The method may further include the step of refining the epoxy resin as a raw material, as mentioned briefly above, prior to the step of manufacturing the subject including the silicon hybrid (Si-hybrid) epoxy resin. Specifically, in the market, an epoxy resin raw material containing, as a balance, a compound containing 80% by weight to 90% by weight of a compound having n = 0 in the above formula (1) and having n of 1 or more relative to the total amount (100% Can be obtained. When the epoxy resin raw material is purified by using a molecular thin-film distillation apparatus, 98% by weight to 90% by weight of a compound having n = 0 in the formula (1) is added to the total amount of the purified product (100% 1 or more as the balance, the purity of the compound having n = 0 in the above formula (1) is improved to 98% or more. Of course, if the raw material of the epoxy resin having a purity of 98% or more of the compound of n = 0 in the formula 1 is obtained on the market, the purification step may be omitted.

Mixing process

No particular method is required for the mixing of the subject and the curing agent. In other words, simply mixing the above-mentioned subject and the above-mentioned curing agent can yield a resin composition which can be prepared as a cured product by thermosetting.

However, depending on the properties of the desired cured product, the mixing ratio of the above-mentioned curing agent and the above-mentioned curing agent may be varied, and the mixing ratio thereof is as described above.

Cured goods  And a material containing the same

In still another embodiment of the present invention, there is provided a cured product of the above-mentioned thermosetting resin composition and a material containing the same. The above-mentioned thermosetting resin composition can be thermoset with a thermosetting method and conditions generally known in the art, and the thermosetting resin can be embodied in various materials.

As described above, the above-mentioned cured product of the thermosetting resin composition may have various physical properties depending on the blending ratio of the raw materials.

Visible light transmittance, Y.I.

Basically, irrespective of the raw material blending ratio, the visible ray wavelength range (transmittance in the range of 380 to 420 nm is 90% or more and YI (Yellow Index) value according to ASTM standard) can be 0.6 or less in the state of not exposed to ultraviolet rays. Furthermore, even after exposure to ultraviolet light, the transmittance of the visible ray wavelength band (380 to 420 nm region) is maintained at 90% or more, and yellowing (i.e., change in YI value) can be suppressed compared with a generally known epoxy resin- connect.

Strain due to external impact (Ball-drop test)

On the other hand, when the compounding ratio of the composition is limited so as to include the curing agent in an amount of more than 75 parts by weight and less than 90 parts by weight, or more than 95 parts by weight based on 100 parts by weight of the subject, Or may not break.

This can be confirmed from the ball-drop test of the test example described later. Specifically, an external impact may be applied to the cured specimen when it drops 22 grams of ball at a height of 50 cm from the floor toward the cured specimen secured to the floor. After 10 external impacts (ie, ball-drop) were applied, it was confirmed that there was very little or no cracking and warping of the hard specimen after the visual inspection.

Self-restitution by external energy (heat)

Furthermore, when the compounding ratio of the composition is limited so as to include the curing agent in an amount of more than 75 parts by weight and less than 90 parts by weight with respect to 100 parts by weight of the subject, the cured product may have self-resilience by external energy (heat).

When calculating the restoration ratio according to the following formula 1, the restoration ratio according to the following formula 1 may be 60% or more, specifically 90% or more, for the cured product at this time. Specifically, the restoration ratio according to the following formula (1) is obtained by bending the cured specimen at 180 degrees and then measuring the angle at which the restored one is left at room temperature for one hour based on the angle (i.e., initial bending angle, 180 degrees) (D ').

[Formula 1]

Recovery rate (%) = 100 * [D '/ 180]

(D '= bending angle of specimen after left for 1 hour at room temperature)

Flexural Strength and Tensile Strength

In addition, when the compounding ratio of the composition is limited so as to include the curing agent in an amount of more than 75 parts by weight and less than 90 parts by weight with respect to 100 parts by weight of the subject, the cured product has a low flexural strength, The strength change may be small.

The flexural strength at this time may be 1,600 MPa or less when the flexural modulus according to the ASTM standard at room temperature is measured and the flexural strength change ratio according to the following formula 2 and the tensile strength according to the following formula 3 ) Is measured.

[Formula 2]

Change ratio of flexural modulus (%) = 100 * [(bending strength at room temperature) - (bending strength at 70 占 폚)] / (bending strength at room temperature)

In the formula 2, flexural strength according to the ASTM standard is substituted at normal temperature and 70 캜.

 [Formula 3]

Change rate of tensile strength (%) = 100 * [(tensile strength at room temperature) - (tensile strength at 70 占 폚)] / (tensile strength at room temperature)

In the above formula 3, the tensile strength according to the ASTM standard is substituted at normal temperature and 70 ° C.

variety Material with properties  avatar

The above-mentioned thermosetting resin composition can be easily realized as a material having a film or a thin film form by applying a constant surface pressure and a temperature condition and thermally curing it.

This can be widely applied as a transparent substrate, an exterior material, or a protective material of an electronic device, and a desired property can be realized by controlling the composition ratio of the composition according to the application field.

In embodiments of the present invention, a thermosetting resin composition is formed using an epoxy resin hybridized with an inorganic element and an acid anhydride modified with glycol, and a cured product is obtained from such a composition , And can be used as an appropriate material.

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.

Manufacturing example  1: High purity Bisphenol-based  Preparation of epoxy resin

A bisphenol-based epoxy resin composition comprising about 85% by weight of a compound having n = 0 in the following formula (1) (i.e., a compound represented by the following formula (1-1) (Kudo Chemical Co., Ltd., product name: YD-128) containing other inevitable chlorine (Cl) based impurities were prepared.

[Chemical Formula 1]

[Formula 1-1]

The bisphenol-based epoxy resin raw material (YD-128) is distilled at a high vacuum (0.02 mbar or less) / high temperature (190 to 240 ° C) using a molecular thin-film distillation apparatus, , About 98% by weight or more of a compound represented by the following formula (1-1), and the remainder is a compound of 1? N in the above formula (1) and other inevitable chlorine (Cl) Based epoxy resin (KODO CHEMICAL CO., LTD., Product name: KDS-8128).

The bisphenol-based epoxy resin (KDS-8128) purified with high purity has an epoxy equivalent of 170 to 175 g / eq, a content of chlorine compound impurity (Total Chlorine, T-Cl) of 700 ppm or less, Gardner of 0.1 or less, Of the viscosity is 4,000 cps or less.

Manufacturing example  2: Manufacture of the subject

(High purity Bisphenol-based  Epoxy resins and silicon intermediates Thermal polymerization )

The high-purity bisphenol-based epoxy resin (KDS-8128) and a silicon intermediate (Si-intermediate, Xiameter, product name: RSN-6018) represented by the following formula 2 were blended at a weight ratio of 9: 1, For 4 hours to obtain a transparent product with an epoxy equivalent of 195 g / eq, a viscosity of 8,000 cps, a T-Cl of 600 ppm or less, Gardner 0.1. The product thus obtained was the subject of Production Example 4 to be described later.

(2)

Manufacturing example  3: Preparation of hardener

(New Japan Chemical Co., Ltd., product name: MH-700G) mixed with acid anhydride represented by the following formula (3-1) and acid anhydride represented by the following formula (3-2) and polyethylene glycol 9: 1, and the mixture was stirred under a nitrogen atmosphere at 120 ° C for 4 hours to obtain a product having an acid anhydride equivalent of 195 g / eq. The obtained product was used as the curing agent of Production Example 4 described later.

[Formula 3-1]

[Formula 3-2]

[Chemical Formula 4]

(단, n=~90이다)

(Where n = 90)

Example

The product (preparation) of Preparation Example 2 and the product (preparation) of Preparation Example 3 were compounded in the respective equivalent ratios (phr) shown in Table 1 below, and a phosphine-based catalyst (Quanternary phosphonium bromide) was added , Each thermosetting composition was prepared.

However, the equivalence ratio (phr) in the following Table 1 is based on 100 parts by weight of the product (preparation) of Production Example 2, the amount (weight portion) of the product (curing agent) of Production Example 3 and the addition amount of the phosphine- (Parts by weight). (Specifically, in Table 1 below, the amount of the phosphine-based catalyst to be added is 0.1 times the amount (parts by weight) of the product (curing agent) of Production Example 3)

Each of the thermosetting compositions was cured according to the following series of conditions using a press curing apparatus to obtain respective cured specimens.

1 ^st step: 90 ° C x 2hr, vacuum degree 15 torr, surface pressure 12.5 kg / f

2 ^nd step: 120 캜 x 2 hr, normal pressure, surface pressure 12.5 kg / f

3 ^rd step: 150 ° C x 1hr, normal pressure, surface pressure 12.5 kg / f

Test Example

Each of the cured specimens obtained in Production Example 4 was cut to a width of 10 mm, a length of 100 mm and a thickness of 4 mm, and various properties were measured according to the ASTM standard as follows. Respectively.

1) Glass Transition Temperature (Tg): The glass transition temperature of the cured specimen was measured using differential scanning calorimetry (DSC).

 2) Mechanical properties: The flexural modulus, tensile strength, and Young's modulus of the cured specimens were measured at room temperature and 70 ° C using a universal fatigue tester.

3) Optical properties: The transmittance, turbidity, and Y.I of visible light (wavelength: 390 to 420 nm) were measured before and after ultraviolet exposure of the hardened specimen, respectively. Here, the ultraviolet ray exposure is performed by using a UV lamp (B type) and exposing the cured specimen to a 15W output for 72 hours.

4) Ball-drop test: At a height of 50 cm from the bottom, a 22 g ball is dropped 10 times against the hardened specimen fixed on the floor, and then the specimen is cracked and warped. And it was classified by pass / fail according to whether crack occurred or not.

Item unit A B C D E F G H Compounding ratio of hardener phr 110 105 100 95 90 85 80 75 Catalyst mixing ratio phr 0.11 0.105 0.1 0.095 0.09 0.085 0.08 0.075 Optical property Before UV exposure Transmittance % 94.06 93.27 92.62 91.21 92.02 92.27 91.97 92.05 Turbidity % 11.50 15.38 4.25 9.88 3.77 7.4 3.49 4.63 Y.I. - 0.08 0.81 0.59 0.09 0.68 0.37 0.66 0.52 After UV exposure Transmittance % 93.29 92.65 92.16 91.82 91.72 91.32 91.65 91.67 Turbidity % 11.88 25.98 4.04 6.22 4.04 7.25 3.47 3.86 Y.I. - 2.12 8.61 8.38 4.64 3.53 2.50 2.96 2.30 Thermal properties Tg ℃ 85.3 24.9 39.3 22.6 71.6 60 70 61 Mechanical properties Room temperature Flexural Modulus MPa 3910 - 1490 - 2160 3240 - - Tensile strength Kgf / cm ² 391 7.81 90 55 341 725 807 753 Young's modulus MPa 1835 2.03 955 392 1140 1645 1659 1659 70 ℃ Tensile strength Kgf / cm ² 279 0.04 6.92 5.6 10 725 807 753 Young's modulus MPa 1192 2.12 3.53 1.1 3.7 14.3 429 28 Ball drop crarking Fail Fail pass Fail Fail pass pass Fail

Based on the evaluation results shown in Table 1, the following calculation / evaluation was carried out, and the results are shown in Table 2.

Reconstruction ratio: in terms of from 70 ℃, forward bending desk (bending test, bending condition) of the cured product specimen, and allowed to stand at room temperature for 1 hour and then measuring the angle to be restored with respect to the bending point, according to the following formula 1 reconstruction ratio Respectively.

[Formula 1]

Recovery rate (%) = 100 * [D '/ 180]

D '= bending angle of specimen after leaving for 1 hour at room temperature

In the above formula (1), D 'is a value obtained by bending test at 70 ° C and room temperature, leaving at room temperature for 1 hour, and then measuring the angle restored to the bending point.

Flexural Modulus Change Rate : Calculated according to Equation 2 below.

[Formula 2] Rate of change of flexural modulus (%) = 100 * [(room temperature bending strength) - (70 占 폚 bending strength)] / (room temperature bending strength)

Rate of change of tensile strength: Calculated according to the following formula 3.

(3) Tensile strength change rate (%) = 100 * [(normal temperature tensile strength) - (70 占 폚 tensile strength)] / (normal temperature tensile strength)

Item Young's Modulus Tensile strength Recovery rate Temperature Room temperature 70 ℃ Rate of change Room temperature 70 ℃ Rate of change A 1835 Mpa 1192 Mpa 35% 391 Kgf / cm ² 279 Kgf / cm ²  28% Not measurable B 2.03 Mpa 2.12 MPa Not measurable 7.81 Kgf / cm ² 0.04 Kgf / cm ²  99% Not measurable C 1010 Mpa 3.53 Mpa  99% 90 Kgf / cm ² 6.92 Kgf / cm ² 92% ~ 90% D 392 Mpa 1.1 MPa  99% 55 Kgf / cm ² 5.6 Kgf / cm ² Not measurable Not measurable E 1140 Mpa 3.7 MPa  99% 341 Kgf / cm ² 10 Kgf / cm ²  97% ~ 50% F 1645 Mpa 10.3 Mpa  99% 725 Kgf / cm ² 14.3 Kgf / cm ² 98% Not measurable G 1659 Mpa 1373 Mpa  17% 807 Kgf / cm ² 429 Kgf / cm ² 46% Not measurable H 1659 Mpa 16 Mpa 99% 753 Kgf / cm ² 28 Kgf / cm ² 96% Not measurable

Referring to Tables 1 and 2, it can be confirmed that the physical properties of the cured product vary depending on the blending ratio of the product (preparation) of Production Example 2 and the product (preparation) of Production Example 3. This means that the compounding ratio of the product (preparation) of Production Example 2 and the product (preparation) of Production Example 3 can be selected according to the properties of the desired material.

Specifically, in Table 1, it can be confirmed that the visible light transmittance before and after ultraviolet exposure of all the hardener specimens is 90% or more. That is, when a cured product is prepared by blending the product (the subject) of Production Example 2 and the product (curing agent) of Production Example 3 within the range of 110 to 75 parts by weight, even after exposure to ultraviolet rays, % Or more visible light transmittance can be ensured. Therefore, when a product (a subject) of Production Example 2 and a product (a curing agent) of Production Example 3 are blended, a material having a high transparency (a cured product) can be basically realized.

Further, in Table 1, it can be confirmed that the cured specimens A, B, D, E, and H did not pass the ball-drop test but the remaining cured specimens C, F, Therefore, the compounding ratio (phr) of the product (preparation) of Production Example 2 and the product (preparation) of Production Example 3 (phr) was less than 105 and less than 95 in the range excluding the blending ratio of the cured product specimens A, B, D, E, , Or less than 90 and less than 75, it can be realized as a material (cured product) having high transparency and less damage by external physical force.

In particular, in Tables 1 and 2, in the case of the cured specimen C, cracks and warpage hardly occurred during the ball-drop test, and the flexural modulus at room temperature was 1,600 MPa or less, Or more. The mixing ratio (phr) of the product (preparation) of Production Example 2 and the product (curing agent) of Production Example 3 (phr) was set within the range excluding the compounding ratio of the cured product specimens A, B, D, E, F, G, Is less than 105 and less than 95, it is possible to obtain a material having a high transparency, less damage due to external physical force, and a material capable of self-recovery according to a change in temperature even when damage is caused by external physical force ). ≪ / RTI >

On the other hand, in Tables 1 and 2, in the case of the cured specimens F and G, although the restoration ratio according to the temperature change is lower than that of the cured specimen C, based on the ball-drop test, And the like.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (21)

A subject comprising a silicon-hybrid (Si-hybrid) epoxy resin, and
An acid anhydride (B1) comprising a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2); And a curing agent comprising a glycol-modified acid anhydride (B2) in which a part of carboxylic acid anhydride functional groups in the acid anhydride (B1) is modified with a glycol functional group.
Thermosetting resin composition:
[Formula 3-1]

[Formula 3-2]

The method according to claim 1,
The above-
Epoxy resin (A1); And
And a silicone hybrid (Si-hybrid) epoxy resin (A2) in which part or all of the epoxy functional groups in the epoxy resin (A1) are substituted with silicon (Si).
Thermosetting resin composition.
3. The method of claim 2,
The above-mentioned epoxy resin (A1)
1. A compound represented by the following formula (1): < EMI ID =
Thermosetting resin composition:
[Chemical Formula 1]

In Formula 1,
n is a number from 0 to 0.85.
The method of claim 3,
The silicon hybrid (Si-hybrid) epoxy resin (A2)
Wherein part or all of the epoxy functional groups in the epoxy resin represented by the above formula (1) are substituted with silicon (Si)
Thermosetting resin composition.
5. The method of claim 4,
The silicon hybrid (Si-hybrid) epoxy resin (A2)
A silicone-based compound, and a thermal polymer of an epoxy resin represented by the above formula (1)
Thermosetting resin composition.
6. The method of claim 5,
The silicon-
Wherein R < 1 >
Thermosetting resin composition:
(2)

In Formula 2,
R is the same or different from each other and is a substituted or unsubstituted C1 to C6 alkyl; or. Substituted or unsubstituted phenyl;
3. The method of claim 2,
The silicone hybrid (A2) is contained in an amount of 10 to 80% by weight with respect to the total amount of the subject (100% by weight), and the balance includes the epoxy resin (A1) and other unavoidable impurities sign,
Thermosetting resin composition.
delete delete The method according to claim 1,
The glycol-modified acid anhydride (B2)
(3-1), the compound represented by the formula (3-2), and the glycol compound.
Thermosetting resin composition.
11. The method of claim 10,
The above-mentioned glycol-
Wherein R < 1 >
Thermosetting resin composition:
[Chemical Formula 4]

In the formula (4), n is a number of 9 to 230.
The method according to claim 1,
For 100 parts by weight of the subject,
Wherein the curing agent is contained in an amount of 75 parts by weight or more and 110 parts by weight or less.
Thermosetting resin composition.
The method according to claim 1,
For 100 parts by weight of the subject,
Wherein the curing agent is contained in an amount of more than 75 parts by weight, and less than 90 parts by weight, or more than 95 parts by weight,
Thermosetting resin composition.
The method according to claim 1,
For 100 parts by weight of the subject,
Wherein the curing agent is contained in an amount of more than 75 parts by weight and less than 90 parts by weight.
Thermosetting resin composition.
The method according to claim 1,
A diluent solvent, a thermosetting catalyst, or a mixture thereof.
Thermosetting resin composition.
Applying heat to a mixture comprising an epoxy resin and a silicone compound to produce a subject comprising a silicon-hybrid epoxy resin,
An acid anhydride (B1) comprising a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2); And a glycol compound, to produce a curing agent, and
Mixing the subject and the curing agent to obtain a thermosetting resin composition,
In the step of preparing the curing agent, the acid anhydride (B1); And a glycol-modified acid anhydride (B2) in which a part of the carboxylic acid anhydride functional group in the acid anhydride (B1) is modified with a glycol functional group.
Method of producing thermosetting resin composition:
[Formula 3-1]

[Formula 3-2]

17. The method of claim 16,
Preparing a subject comprising the silicon hybrid (Si-hybrid) epoxy resin,
And further comprising the step of purifying the epoxy resin.
A method for producing a thermosetting resin composition.
18. The method of claim 17,
The step of purifying the epoxy resin comprises:
Lt; RTI ID = 0.0 > molecular < / RTI > thin film distillation apparatus.
A method for producing a thermosetting resin composition.
A material comprising a cured product of the thermosetting resin composition according to claim 1.
20. The method of claim 19,
A material in the form of a film or a thin film.
21. The method of claim 20,
Materials that are transparent substrates, exterior materials, or protective materials for electronic devices.