KR102548181B1 - An end-capped isocyanate prepolymer composition capable of providing adhesive with improved adhesiveness and impact resistance and an adhesion promoter for epoxy resin comprising the same, and an epoxy resin composition comprising the adhesion promoter and an adhesive comprising the same - Google Patents

Abstract

The present invention relates to an end-capped isocyanate prepolymer composition and its use, and more particularly, to anhydrous sugar alcohols, dianhydrosugar alcohols, polysaccharide alcohols, anhydrosugar alcohols derived from polysaccharide alcohols, and non-hydrosugar containing polymers of one or more of these. Isocyanate prepolymer prepared by urethane reaction of a polyisocyanate with a polyol composition comprising an alkylene oxide added to a sugar alcohol composition and an alkylene glycol composition and a polyether polyol in a specific OH equivalent ratio An end-capped isocyanate prepolymer composition prepared by reacting the composition with an end-capping agent, environmentally friendly, and particularly capable of improving the T-peel strength and room temperature impact strength of the bonding site when applied to an epoxy resin composition for bonding, and including the same It relates to an adhesion promoter for epoxy resins, an epoxy resin composition comprising the adhesion promoter, and an adhesive comprising the same.

Description

An end-capped isocyanate prepolymer composition capable of providing an adhesive having improved adhesion and impact resistance, an adhesion promoter for epoxy resin comprising the same, an epoxy resin composition comprising the adhesion promoter, and an adhesive comprising the same isocyanate prepolymer composition capable of providing adhesive with improved adhesiveness and impact resistance and an adhesion promoter for epoxy resin comprising the same, and an epoxy resin composition comprising the adhesion promoter and an adhesive comprising the same}

The present invention relates to an end-capped isocyanate prepolymer composition and its use, and more particularly, to anhydrous sugar alcohols, dianhydrosugar alcohols, polysaccharide alcohols, anhydrosugar alcohols derived from polysaccharide alcohols, and non-hydrosugar containing polymers of one or more of these. Isocyanate prepolymer prepared by urethane reaction of a polyisocyanate with a polyol composition comprising an alkylene oxide added to a sugar alcohol composition and an alkylene glycol composition and a polyether polyol in a specific OH equivalent ratio An end-capped isocyanate prepolymer composition prepared by reacting the composition with an end-capping agent, environmentally friendly, and particularly capable of improving the T-peel strength and room temperature impact strength of the bonding site when applied to an epoxy resin composition for bonding, and including the same It relates to an adhesion promoter for epoxy resins, an epoxy resin composition comprising the adhesion promoter, and an adhesive comprising the same.

Epoxy resins have excellent heat resistance, mechanical properties, electrical properties and adhesion. Epoxy resins take advantage of this characteristic and are used for sealing materials such as wiring boards, circuit boards, multilayered circuit boards, semiconductor chips, coils, and electric circuits. Alternatively, epoxy resin is also used as a resin for adhesives, paints, and fiber-reinforced resins.

Epoxy resins find widespread use as thermosets in many applications. They are used as a thermosetting matrix in prepregs composed of fibers incorporated in a thermosetting matrix. Also, because of their toughness, flexibility, adhesion and chemical resistance, they can be used as materials for surface coatings, for bonding, molding and laminating, all of which are used in aerospace, automotive, electronics, construction, furniture, green energy and sporting goods. Various applications can be found in a wide variety of industries such as industry.

A wide range of epoxy resins are readily available and may be used depending on their reactivity required for a particular application. For example, resins can be solid, liquid or semi-solid, and can have a variety of reactivity depending on the application to which they are applied. The reactivity of epoxy resins is often measured in terms of epoxy equivalent weight, which is the molecular weight of a resin containing a single reactive epoxy group. The lower the epoxy equivalent, the higher the reactivity of the epoxy resin. Different reactivity is required for different epoxy resin applications, depending on whether it is present as a matrix for fiber-reinforced prepregs, adhesive coatings, or structural adhesives.

However, epoxy resin itself is too brittle and has low strength, so its application range is limited, and rubber additives or thermoplastic polymer additives used to compensate for this are not able to form a chemical bond with the epoxy resin, thereby improving corrosion resistance. There is a problem of falling, and the eco-friendliness is poor. Therefore, there is a demand for development of an adhesion promoter that is environmentally friendly and can improve the strength of an epoxy resin.

On the other hand, hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of sugars, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is 2 to 5 It has a chemical formula of (an integer of) and is classified according to carbon atoms into tetratol, pentitol, hexitol, and heptitol (4, 5, 6, and 7 carbon atoms, respectively). Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrous sugar alcohol is a substance formed by removing one or more water molecules from the inside of hydrogenated sugar. When one water molecule is removed, it has the form of tetraol with four hydroxyl groups in the molecule, and two water molecules In the case of removal, it has a diol form with two hydroxyl groups in the molecule, and can be prepared using hexitol derived from starch (e.g., Korean Patent Registration No. 10-1079518, Korean Patent Publication No. 10-2012-0066904). Since anhydrosugar alcohol is an environmentally friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with great interest for a long time. Among these anhydrous sugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

The use of anhydrous sugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, patch adhesives, pharmaceuticals such as mouthwashes, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and has the effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an environmentally friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrous sugar alcohol is receiving a lot of attention due to its various application possibilities, and its use in the actual industry is gradually increasing.

In contrast, in the prior art, special uses such as simply using as a binder for by-products obtained in the process of producing anhydrous sugar alcohol by dehydration of hydrogenated sugar were not considered.

Therefore, there is a need to develop useful uses for by-products obtained in the process of preparing hydrogenated sugar from glucose and anhydrous sugar alcohol from hydrogenated sugar.

An object of the present invention is environmentally friendly because anhydrous sugar alcohol is used, and in particular, when applied to an epoxy resin composition for bonding, T-peel strength (adhesion) and room temperature impact strength (impact resistance) can be improved. , To provide an end-capped isocyanate prepolymer composition, and an adhesion promoter for epoxy resins including the same, and an epoxy resin composition including the adhesion promoter and an adhesive including the same.

A first aspect of the present invention is an end-capped isocyanate prepolymer composition prepared by reacting an isocyanate prepolymer composition with an end capping agent, wherein the isocyanate prepolymer composition includes an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol It is prepared by a urethane reaction of a polyol composition and polyisocyanate, and the anhydrosugar alcohol-alkylene glycol composition is prepared by an addition reaction of anhydrosugar alcohol composition and an alkylene oxide, and the anhydrous sugar alcohol composition is the first to the second 5, wherein the first polyol component is anhydrous sugar alcohol, the second polyol component is anhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth The polyol component of is an anhydrous sugar alcohol formed by removing water molecules from polysaccharide alcohol represented by Formula 1 below, the fifth polyol component is one or more polymers selected from the first to fourth polyol components, and the The ratio of OH equivalents of the polyether polyol to OH equivalents of the sugar alcohol-alkylene glycol composition (OH equivalents of polyether polyol / OH equivalents of anhydrous sugar alcohol-alkylene glycol composition) is greater than 0.25 and less than 9, wherein the wherein the total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) is greater than 1.5 and less than 2.0.

[Formula 1]

In Formula 1, n is an integer from 0 to 4.

A second aspect of the present invention is a method for producing an end-capped isocyanate prepolymer composition, comprising (1) an isocyanate prepolymer composition by urethane-reacting a polyisocyanate with a polyol composition including an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol Preparing; and (2) reacting the isocyanate prepolymer composition obtained in step (1) with an end capping agent, wherein the anhydrosugar alcohol-alkylene glycol composition is formed by an addition reaction between the anhydrosugar alcohol composition and alkylene oxide. prepared, wherein the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is a polysaccharide alcohol represented by Formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, and the fifth polyol component is the first to fourth polyol components. It is at least one polymer selected from polyol components of, and the ratio of the OH equivalent of the polyether polyol to the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition (OH equivalent of polyether polyol / anhydrous sugar alcohol-alkylene glycol OH equivalents of the composition) is greater than 0.25 and less than 9, and the total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) are greater than 1.5 and less than 2.0. A method for preparing the composition is provided.

A third aspect of the present invention provides an adhesion promoter for epoxy resin comprising the end-capped isocyanate prepolymer composition according to the first aspect of the present invention.

A fourth aspect of the present invention is an adhesion promoter for epoxy resins according to the third aspect of the present invention; It provides an epoxy resin composition comprising a; and an epoxy resin.

A fifth aspect of the present invention provides an adhesive comprising the epoxy resin composition according to the fourth aspect of the present invention.

The end-capped isocyanate prepolymer composition according to the present invention is environmentally friendly, and in particular, when applied to an epoxy resin composition for bonding, the T-peel strength (adhesiveness) and room temperature impact strength (impact resistance) of the bonding site can be improved compared to conventional products. can

In addition, since the end-capped isocyanate prepolymer composition according to the present invention is prepared from an anhydrosugar alcohol composition, which is a polyol composition obtained by utilizing a by-product obtained in the process of preparing an internal dehydration product of hydrogenated sugar, economic feasibility is improved and the problem of by-product disposal is solved. Accordingly, environmental friendliness can be improved.

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

[End-capped isocyanate prepolymer composition and manufacturing method thereof]

The end-capped isocyanate prepolymer composition of the present invention is prepared by reacting an isocyanate prepolymer composition prepared by urethane-reacting a polyisocyanate with a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol, and an end capping agent, , Here, the ratio of the OH equivalent of the polyether polyol to the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition (OH equivalent of polyether polyol / OH equivalent of anhydrosugar alcohol-alkylene glycol composition) is greater than 0.25 to is less than 9, and the total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) is greater than 1.5 and less than 2.0.

Anhydrous Sugar Alcohol Composition

In the present invention, “anhydrous sugar alcohol” is generally referred to as hydrogenated sugar or sugar alcohol, which is obtained by adding hydrogen to a reducing end group of sugars by removing one or more water molecules from the compound. means any material obtained.

The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is the first to fourth polyol components It is one or more polymers selected from

[Formula 1]

In Formula 1, n is an integer from 0 to 4.

Anhydrous sugar alcohol, which is the first polyol component included in the anhydrous sugar-alcohol composition of the present invention; dianhydrosugar alcohol as a second polyol component; a polysaccharide alcohol as a third polyol component; anhydrous sugar alcohol formed by removing water molecules from polysaccharide alcohol, which is the fourth polyol component; And at least one, preferably two or more, more preferably all of one or more polymers selected from the first to fourth polyol components that are the fifth polyol component, a glucose-containing saccharide composition (e.g., glucose mannose; fructose; and a saccharide composition including disaccharide or higher polysaccharides including maltose) to prepare a hydrogenated sugar composition, dehydration reaction by heating the obtained hydrogenated sugar composition under an acid catalyst, and dehydration reaction obtained It can be obtained in the process of preparing the product by thin film distillation. More specifically, all of the first to fifth polyol components included in the anhydrous sugar alcohol composition of the present invention may be by-products remaining after obtaining a thin film distillate by thin film distillation of the obtained dehydration reaction product.

Monohydrosugar alcohol, which is the first polyol component, is anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of monohydrosugar alcohol is not particularly limited, but may preferably be monohydrosugar hexitol, more specifically 1,4-anhydrohexitol, 3,6-anhydrohexitol , 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

The second polyol component, dianhydrosugar alcohol, is anhydrosugar alcohol formed by removing two water molecules from the inside of hydrogenated sugar, and has a diol form with two hydroxyl groups in the molecule. can be used to manufacture. Since imudang alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with much interest for a long time. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

In the present invention, the type of dianhydrosugar alcohol is not particularly limited, but may be preferably dianhydrosugar hexitol, and more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

In one embodiment, the polysaccharide alcohol represented by Chemical Formula 1, which is the third polyol component, may be prepared from a hydrogenation reaction of disaccharides or higher polysaccharides including maltose.

In one embodiment, the anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, which is the fourth polyol component, is a compound represented by Formula 2, a compound represented by Formula 3, or a mixture thereof. can be selected from:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer of 0 to 4.

In one embodiment, the at least one polymer selected from the first to fourth polyol components, which is the fifth polyol component, includes at least one selected from the group consisting of condensation polymers prepared from the following polycondensation reaction. can do:

- polycondensation reaction of the first polyol component,

- polycondensation reaction of the second polyol component,

- polycondensation reaction of the third polyol component,

- polycondensation reaction of the fourth polyol component,

- polycondensation reaction between the first polyol component and the second polyol component;

- polycondensation reaction between the first polyol component and the third polyol component;

- polycondensation reaction between the first polyol component and the fourth polyol component;

- polycondensation reaction between the second polyol component and the third polyol component;

- polycondensation reaction between the second polyol component and the fourth polyol component;

- polycondensation reaction between the third polyol component and the fourth polyol component;

- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component,

- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component,

- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component,

- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or

- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component.

In one embodiment, the anhydrous sugar alcohol composition may satisfy the following i) to iii):

i) the number average molecular weight (Mn) of the anhydrous sugar alcohol composition is 193 to 1,589 g/mol;

ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41;

iii) The average number of -OH groups per molecule in the anhydrous sugar alcohol composition is 2.54 to 21.36.

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the anhydrous sugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more or 208 or more, and also 1,589 or less, 1,560 or less , 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less. Also, in one embodiment, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, and more specifically As may be 202 to 1,500, more specifically may be 205 to 1,490. If the number average molecular weight of the anhydrous sugar alcohol composition is less than 193, compatibility between the anhydrosugar alcohol-alkylene glycol composition and the polyisocyanate prepared therefrom may deteriorate, and conversely, if it exceeds 1,589, end capping prepared using this When the isocyanate prepolymer composition is used as an adhesion promoter for epoxy resin, there is no effect of improving additional physical properties, but economic feasibility may decrease due to an increase in material cost.

In one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more or 1.25 or more, and also 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less. In addition, in one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and more Specifically, it may be 1.20 to 3.25, and more specifically, it may be 1.23 to 3.22. If the polydispersity index of the anhydrous sugar alcohol composition is less than 1.13, the compatibility between the anhydrosugar alcohol-alkylene glycol composition and the polyisocyanate prepared therefrom may deteriorate, and conversely, the polydispersity index of the anhydrosugar alcohol composition is 3.41 If it exceeds, when using the end-capped isocyanate prepolymer composition prepared using the same as an adhesion promoter for an epoxy resin, there is no effect of improving physical properties, and economic feasibility may decrease due to an increase in material cost.

In one embodiment, the average number of -OH groups per molecule in the anhydrous sugar alcohol composition may be 2.54 or more, 2.60 or more, 2.65 or more, 2.70 or more, 2.75 or more, or 2.78 or more, and also 21.36 It may be less than or equal to 21.30, less than or equal to 21.0, less than or equal to 20.5, less than or equal to 20.0, less than or equal to 19.95 or less than or equal to 19.92. Also, in one embodiment, the average number of —OH groups per molecule in the anhydrous sugar alcohol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and more specifically 2.65 to 21.30. It may be 21.0. If the average number of -OH groups per molecule in the anhydrous sugar alcohol composition is less than 2.54, when the end-capped isocyanate prepolymer composition prepared using this is used as an adhesion promoter for epoxy resin, there is no effect of improving physical properties, and the material cost increases. Conversely, if the average number of -OH groups per molecule in the anhydrous sugar alcohol composition exceeds 21.36, the compatibility between the anhydrosugar alcohol-alkylene glycol composition and polyisocyanate prepared therefrom may deteriorate. .

In one embodiment, in the anhydrous sugar alcohol composition, based on the total weight of the composition, for example, the first polyol component is 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight , and the second polyol component may be included in 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, and the third polyol component and the fourth polyol The total content of the components may be 0.1 to 6.5% by weight, specifically 0.5 to 6.4% by weight, more specifically 1 to 6.3% by weight, and the fifth polyol component may be 55 to 90% by weight, specifically 60 to 6.3% by weight 89.9% by weight, more specifically may be included in 70 to 89.9% by weight, but is not particularly limited thereto.

In one embodiment, the anhydrosugar alcohol composition is a glucose-containing saccharide composition (eg, glucose; mannose; fructose; and a saccharide composition comprising disaccharides or higher polysaccharides including maltose) by hydrogenation reaction to prepare a hydrogenated sugar composition , The obtained hydrogenated sugar composition may be dehydrated by heating under an acid catalyst, and the obtained dehydration reaction product may be prepared by thin film distillation, more specifically, thin film distillate obtained by thin film distillation of the obtained dehydration reaction product After that, it may be the remaining by-product.

More specifically, a hydrogenation reaction is performed on the glucose-containing saccharide composition under a hydrogen pressure of 30 to 80 atm and a heating condition of 110° C. to 135° C. to prepare a hydrogenated sugar composition, and the obtained hydrogenated sugar composition is dehydrated. The reaction is carried out under reduced pressure conditions of 1 mmHg to 100 mmHg and heating conditions of 105 ° C to 200 ° C to obtain a dehydration reaction product, and thin film distillation of the obtained dehydration reaction product is performed under reduced pressure conditions of 2 mbar or less and 150 ° C to 175 ° C It may be performed under heating conditions of, but is not limited thereto.

In one embodiment, the glucose content of the glucose-containing saccharide composition may be 41% by weight or more, 42% by weight or more, 45% by weight or more, 47% by weight or more, or 50% by weight or more, based on the total weight of the saccharide composition. 99 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less, or 97 wt% or less, such as 41 to 99.5 wt%, 45 to 98.5 wt%, or 50 to 98 wt%. may be %.

In one embodiment, the content of the polysaccharide alcohol (disaccharide or higher saccharide alcohol) contained in the hydrogenated sugar composition is the total dry weight of the hydrogenated sugar composition (here, the dry weight means the weight of solids remaining after water is removed from the hydrogenated sugar composition) Based on), it may be 0.8% by weight or more, 1% by weight or more, 2% by weight or 3% by weight or more, and 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

Addition reaction of alkylene oxide and its composition with anhydrous sugar alcohol

In the present invention, the "anhydrosugar alcohol-alkylene glycol composition" is prepared by an addition reaction of the anhydrous sugar alcohol composition of the present invention and alkylene oxide.

That is, in the present invention, the anhydrosugar alcohol-alkylene glycol composition includes an adduct obtained by reacting an alkylene oxide with a hydroxyl group at least one terminal of each of the first to fifth polyol components, and specifically, Alkylene oxide adduct of the polyol component of 1 (hereinafter referred to as "first anhydrosugar alcohol-alkylene glycol"), alkylene oxide adduct of the second polyol component (hereinafter referred to as "second anhydrosugar alcohol-alkylene glycol") referred to as "alkylene glycol"), an alkylene oxide adduct of the third polyol component (hereinafter referred to as "third anhydrosugar alcohol-alkylene glycol"), an alkylene oxide adduct of the fourth polyol component ( hereinafter referred to as "fourth anhydrous sugar alcohol-alkylene glycol") and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as "fifth anhydrosugar alcohol-alkylene glycol"). .

In one embodiment, the alkylene oxide may be a C2-C8 linear or C3-C8 branched alkylene oxide, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

According to one embodiment, 100 parts by weight to 500 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition may be added.

If the amount of the alkylene oxide added to 100 parts by weight of the anhydrous sugar alcohol composition is less than 100 parts by weight, the reactivity between the prepared anhydrosugar alcohol-alkylene glycol composition and polyisocyanate decreases, and their reaction may become insufficient. . On the other hand, if the amount of alkylene oxide added to 100 parts by weight of the anhydrous sugar alcohol composition exceeds 500 parts by weight, the prepared anhydrosugar alcohol-alkylene glycol composition is used to prepare an end-capped isocyanate prepolymer composition with an epoxy water When used as an adhesion promoter for paper, the T-peel strength may deteriorate.

In one embodiment, the amount of alkylene oxide added to 100 parts by weight of the anhydrous sugar alcohol composition may be, for example, 100 parts by weight or more, 125 parts by weight or more, 150 parts by weight or more, 175 parts by weight or more, or 200 parts by weight or more , It may also be 500 parts by weight or less, 475 parts by weight or less, 450 parts by weight or less, 425 parts by weight or less, or 400 parts by weight or less, but is not limited thereto.

In one embodiment, the addition reaction of the anhydrous sugar alcohol composition and the alkylene oxide is, for example, 100 ℃ or more, more specifically at a temperature of 100 ℃ to 140 ℃, 1 hour or more, more specifically 1 hour to 1 hour It may be performed for 5 hours, but is not limited thereto.

polyether polyol

In one embodiment, the polyether polyol may include polyalkylene glycol, and more specifically, may include poly(C ₁ -C ₆ )alkylene glycol.

In one embodiment, the polyalkylene glycol may be selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, or a combination thereof.

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the polyether polyol may be 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1,000 or more, and also less than 4,000, 3,900 or less, 3,800 or less, 3,700 or less, 3,600 or less, 3,500 or less, 3,400 or less, 3,300 or less, 3,200 or less, 3,100 or less, or 3,000 or less, but is not limited thereto. Preferably, the number average molecular weight of the polyether polyol may be 500 or more to less than 4,000, or 1,000 to 3,000. If the number average molecular weight of the polyether polyol is too low than the above level, the reaction with polyisocyanate may not proceed, and conversely, if it is too high above the above level, there is no effect of improving additional physical properties, and the economic feasibility may decrease due to the increase in material cost There may be problems.

polyol composition

The polyol composition used in the present invention includes the anhydrous sugar alcohol-alkylene glycol composition and the polyether polyol, wherein the OH equivalent of the polyether polyol with respect to the OH equivalent of the anhydrosugar alcohol-alkylene glycol composition The ratio (OH equivalent of polyether polyol/OH equivalent of anhydrosugar alcohol-alkylene glycol composition) is greater than 0.25 and less than 9.

If the OH equivalent ratio (i.e., OH equivalents of the polyether polyol in the polyol composition/OH equivalents of the anhydrosugar alcohol-alkylene glycol composition) is 0.25 or less, the end-capped isocyanate prepolymer composition prepared using such a polyol composition The molecular weight becomes too large and the viscosity becomes very high, and when this is used as an adhesion promoter, adhesion is poor, such as material peeling (peeling or cracking occurs inside the adhesive), and impact resistance at room temperature is also lowered, resulting in poor impact resistance. It happens.

In addition, when the OH equivalent ratio is 9 or more, the soft portion in the end-capped isocyanate prepolymer composition prepared using such a polyol composition is excessively expressed, resulting in a very low viscosity, and when used as an adhesion promoter, surface peeling (between the adhesive and the adhesive) Peeling occurs at the interface), adhesion deteriorates, room temperature impact strength also decreases, and impact resistance deteriorates.

More specifically, the OH equivalent ratio may be greater than 0.25, greater than 0.26, greater than 0.3, greater than 0.35, greater than 0.4, or greater than 0.43, and may also be less than 9, less than 8.9, less than 8, less than 7, less than 6, less than 5, or less than 4. may, but is not limited thereto.

In one embodiment, the content of the anhydrosugar alcohol-alkylene glycol composition in the polyol composition is 2.5 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, or 5.0 parts by weight or more, based on 100 parts by weight of the polyol composition. part or more, and may also be 46 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 34 parts by weight or less, or 33.5 parts by weight or less, but is not limited thereto.

In one embodiment, the polyether polyol content in the polyol composition may be 54 parts by weight or more, 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, or 66.5 parts by weight or more based on 100 parts by weight of the polyol composition. And, it may also be 97.5 parts by weight or less, 97 parts by weight or less, 96 parts by weight or less, or 95 parts by weight or less, but is not limited thereto.

In one embodiment, the polyol composition may optionally further include a polyol component other than the anhydrosugar alcohol-alkylene glycol composition and polyether polyol.

In one embodiment, the polyol component other than the anhydrosugar alcohol-alkylene glycol composition and polyether polyol is a polyester polyol, a polycaprolactone diol, a polymer polyol obtained by polymerizing these polyols and a vinyl compound, or a combination thereof One selected from the group consisting of can be used. As the vinyl compound, acrylonitrile, styrene, methyl methacrylonitrile, etc. are widely used, and acrylonitrile may be used alone or in combination with styrene.

Urethane reaction of polyisocyanates and polyol compositions therewith

In the present invention, an isocyanate prepolymer composition is prepared by urethane-reacting the polyol composition and polyisocyanate, wherein the total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) are greater than 1.5 to less than 2.0.

If the NCO / OH equivalent ratio (i.e., the total NCO equivalents of the urethane reacted polyisocyanate / the total OH equivalents of the polyol composition) is 1.5 or less, the end-capped isocyanate prepolymer composition prepared using such an isocyanate prepolymer composition is used as an adhesion promoter When used as a furnace, adhesiveness is deteriorated, such as material peeling, and impact resistance at room temperature is also reduced, resulting in poor impact resistance.

In addition, when the NCO / OH equivalent ratio is 2.0 or more, when the end-capped isocyanate prepolymer composition prepared using such an isocyanate prepolymer composition is used as an adhesion promoter, adhesiveness becomes poor, such as surface peeling, and room temperature impact strength and the impact resistance deteriorates.

More specifically, the NCO / OH equivalent ratio may be greater than 1.5, greater than 1.51, greater than 1.53, greater than 1.55, greater than 1.57, greater than 1.59, or greater than 1.6, and also less than 2.0, less than 1.99, less than 1.97, less than 1.95, less than 1.93, It may be 1.91 or less or 1.9 or less, but is not limited thereto.

In the present invention, the polyisocyanate may be used without particular limitation as long as it can be used for producing polyurethane. For example, polyisocyanates selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates, or combinations thereof may be used, and unmodified polyisocyanates may also be used. Both isocyanates or modified polyisocyanates may be used.

In one embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI) (eg, 2,4- or 4,4'-methylenediphenyl diisocyanate), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI), toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI ), phenylene diisocyanate (e.g., 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or 4,4'-dibenzyl diisocyanate. aromatic polyisocyanates; Hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6 -Diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI) (eg 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (eg cyclohexane-1,4-diisocyanate) or ethylene diisocyanate aliphatic polyisocyanates such as the like; Or it may be a combination thereof, but is not limited thereto.

In another embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate Isocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6 -Hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2 ,6-toluene diisocyanate, toluene diisocyanate (2,4-/2,6-isomer ratio = 80/20), diphenylmethane- 2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or combinations thereof, but is not limited thereto. .

More specifically, the polyisocyanate may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

In one embodiment, the urethane reaction may be performed in the presence of a catalyst, such as an amine catalyst, an organometallic catalyst, or a mixture thereof.

The type of the amine catalyst is not particularly limited, but preferably one or a mixture of two or more selected from tertiary amine catalysts may be used, and more specifically, triethylene diamine and triethylamine , N-methyl morpholine, N-ethyl morpholine, or a combination thereof.

The type of the organometallic catalyst is also not particularly limited, but, for example, an organotin catalyst, more specifically, tin octylate, dibutyltin dilaurate (DBTDL), tin bis[2-ethylhexanoate], or a combination thereof. What is selected from the group consisting of can be used.

In one embodiment, the urethane reaction is carried out at an elevated temperature (eg, at 40 to 90 ° C rather than 30 to 100 ° C) for an appropriate time (eg, 0.5 to 5 hours, more specifically 1 to 4 hours) It may be, but is not limited thereto.

End-capping agent and its reaction with the isocyanate prepolymer composition

The end-capped isocyanate prepolymer composition of the present invention is prepared by reacting the isocyanate prepolymer composition with an end capping agent.

In one embodiment, the end-capping agent is one selected from the group consisting of phenol-based compounds, triazine-based compounds, alcohol compounds, amine compounds, benzene-based compounds, dicarboxylic acid ester-based compounds, novolac-based compounds, or combinations thereof More specifically, phenolic compounds (e.g., allylphenol, t-butylphenol, phenol, bisphenol A, bisphenol M, bisphenol F, 1,3-dihydroxybenzene, 1,4-dihydroxy Benzene, 1,2-dihydroxybenzene, phenolphthalein, o,o'-diallylbisphenol A, phenolphthalein, or combinations thereof), benzene-based compounds (e.g., fluoroglucinol, resorcinol, naphthorezo selected from the group consisting of ricinol, or combinations thereof), dicarboxylic acid ester compounds (eg, gallic acid esters, maleic acid esters, or combinations thereof), novolac compounds (eg, cresol novolacs), or combinations thereof It may be one or more, and more specifically, it may be a phenolic compound.

According to one embodiment, 1 equivalent or more (eg, 1 to 2 equivalents, more specifically, 1 to 1.5 equivalents) of an endcapping agent based on 1 equivalent of NCO in the isocyanate prepolymer composition is added under an elevated temperature (eg, 40 to 100 ° C. More specifically, it may be reacted at 40 to 80 ° C.), but is not limited thereto.

In one embodiment, the weight average molecular weight (Mw) of the end-capped isocyanate prepolymer composition of the present invention may be 7,951 to 26,499 g/mol. If the weight average molecular weight of the end-capped isocyanate prepolymer composition exceeds the above range, adhesiveness and impact resistance of an adhesive including the same may be deteriorated.

More specifically, the weight average molecular weight (g / mol) of the end-capped isocyanate prepolymer composition of the present invention may be 7,951 or more, 8,000 or more, 8,100 or more, 8,200 or more, 8,300 or more, 8,400 or more, 8,500 or more, or 8,560 or more, In addition, it may be 26,499 or less, 26,400 or less, 26,300 or less, 26,200 or less, 26,100 or less, 26,000 or less, 25,900 or less, 25,800 or less, or 25,759 or less, but is not limited thereto.

According to another aspect of the present invention, as a method for producing an end-capped isocyanate prepolymer composition, (1) an isocyanate prepolymer composition by urethane-reacting a polyisocyanate with a polyol composition including an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol Preparing; and (2) reacting the isocyanate prepolymer composition obtained in step (1) with an end capping agent, wherein the anhydrosugar alcohol-alkylene glycol composition is formed by an addition reaction between the anhydrosugar alcohol composition and alkylene oxide. prepared, wherein the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is a polysaccharide alcohol represented by Formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, and the fifth polyol component is the first to fourth polyol components. It is at least one polymer selected from polyol components of, and the ratio of the OH equivalent of the polyether polyol to the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition (OH equivalent of polyether polyol / anhydrous sugar alcohol-alkylene glycol OH equivalents of the composition) is greater than 0.25 and less than 9, and the total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) are greater than 1.5 and less than 2.0. A method of making the composition is provided.

In the method for producing the end-capped isocyanate prepolymer composition, the first to fifth polyol components and an anhydrosugar alcohol composition containing them; alkylene oxides and their addition reactions; anhydrosugar alcohol-alkylene glycol compositions and polyether polyols and polyol compositions containing them; urethane reactions of polyisocyanates and polyol compositions therewith; The end capping agent and the reaction of the isocyanate prepolymer composition therewith have been described above.

[Adhesion promoter for epoxy resin, epoxy resin composition and adhesive]

The present invention also provides an adhesion promoter for epoxy resin comprising the above-described end-capped isocyanate prepolymer composition of the present invention.

The present invention also relates to an adhesion promoter for the above epoxy resin; It provides an epoxy resin composition comprising a; and an epoxy resin.

The present invention also provides an adhesive comprising the above epoxy resin composition.

The epoxy resins may be solid, liquid or semi-solid, and may have various reactivity depending on the application to which they are applied. The reactivity of epoxy resins is often measured in terms of epoxy equivalent weight, which is the molecular weight of a resin containing a single reactive epoxy group. The lower the epoxy equivalent, the higher the reactivity of the epoxy resin.

In one embodiment, the epoxy resin includes bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolak-type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-dicyclic epoxy resin, It may be selected from the group consisting of glycidyl ester-type epoxy resin, brominated epoxy resin, biomass-derived epoxy resin, epoxidized soybean oil, or a combination thereof, but is not limited thereto. Preferably, a biomass-derived epoxy resin (eg, diglycidyl ether isosorbide, etc.) may be used in terms of environmental friendliness.

In another embodiment, the epoxy resin is a novolac-type epoxy resin such as a phenol novolac-type epoxy resin or a cresol novolac-type epoxy resin, a bisphenol-type epoxy resin such as a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin, Aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, and aminophenol-type glycidylamine; Quinone type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, triphenolpropane type epoxy resin, alkyl modified triphenolmethane type epoxy resin, triazine nucleus containing epoxy resin, dicyclopentadiene Modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin having a phenylene and/or biphenylene skeleton, naphthol aralkyl type epoxy resin having a phenylene and/or biphenylene skeleton, etc. aralkyl-type epoxy resins, vinylcyclohexene dioxide, dicyclopentadiene oxide, aliphatic epoxy resins such as alicyclic epoxies such as alicyclic diepoxy-adipade, or combinations thereof, but may be selected from the group consisting of, Not limited to this.

In another embodiment, the epoxy resin is a bisphenol F-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolak-type epoxy resin, a biphenyl-type epoxy resin, a stilbene-type epoxy resin, a hydroquinone-type epoxy resin, naphthalene Skeleton type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, diglycy of bisphenol A ethylene oxide adduct Glycidyl ethers having one epoxy group such as diglycidyl ether, diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether, and cresyl glycidyl ether; these Nuclear hydrogenated epoxy resins, which are nuclear hydrogenation products of epoxy resins, or those selected from the group consisting of combinations thereof, are not limited thereto.

In one embodiment, the adhesion promoter for epoxy resins of the present invention may consist only of the end-capped isocyanate prepolymer composition of the present invention.

In another embodiment, the adhesion promoter for epoxy resins of the present invention may further include an additional adhesion promoter component in addition to the end-capped isocyanate prepolymer composition of the present invention within the range capable of achieving the object of the present invention, , As the additional adhesion promoter component, an adhesion promoter component usable for epoxy resins may be used.

In one embodiment, as the additional adhesion promoter component, a polyurethane-modified epoxy resin, a polyurethane-modified silyl epoxy resin, or a combination thereof may be used, but is not limited thereto.

When the adhesion promoter for an epoxy resin comprising the end-capped isocyanate prepolymer composition according to the present invention is used together with an epoxy resin, as well as when a conventional petroleum-based epoxy resin is used alone as the epoxy resin, biomass-derived epoxy Even when a resin is used alone or a mixture of a biomass-derived epoxy resin and a petroleum-based epoxy resin is used, since the epoxy resin composition can exhibit excellent adhesiveness and impact resistance, the epoxy resin composition according to the present invention is environmentally friendly. It can be used as an adhesive.

In one embodiment, the epoxy resin composition of the present invention, in addition to the above-described adhesion promoter for epoxy resin and the epoxy resin, may further include at least one selected from a curing agent, a curing accelerator, a filler, an impact modifier, or a combination thereof. .

As the curing agent, curing agents commonly used in this field may be used alone or in combination of two or more, for example, amines such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, and dimethylcyclohexylamine. compounds (eg, tertiary amines); imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole; organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate and aluminum acetylacetone complex; quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; boron compounds such as boron trifluoride and triphenylborate; metal halides such as zinc chloride and stannous chloride; latent curing agents (e.g., dicyandiamide, high melting point dispersion type latent amine adducts obtained by adding amine to an epoxy resin, etc.; microcapsule type latent curing agents obtained by coating the surface of an imidazole-based, phosphorus-based, or phosphine-based accelerator with a polymer; Amine salt-type latent curing agents; high-temperature dissociation-type thermal cationic polymerization-type latent curing agents such as Lewis acid salts and Bronsted acid salts), or those selected from the group consisting of combinations thereof, but are not limited thereto.

In one embodiment, as the curing agent, one selected from the group consisting of an amine compound, an imidazole compound, an organic phosphorus compound, a latent curing agent, or a combination thereof may be used.

Room temperature curing of epoxy resin usually requires a temperature of 15 ° C or higher and a curing time of 24 hours or more, so fast curing and low-temperature curing are sometimes necessary.

Therefore, for a curing accelerating effect, the epoxy resin composition of the present invention may further include a curing accelerator. Examples of the curing accelerator include urea-based compounds, thiourea-based compounds, Lewis acid-based compounds, or mixtures thereof, and specifically, butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like. Examples include, but are not limited to.

When the curing accelerator is included in the epoxy resin composition of the present invention, the amount used may be 0.01 part by weight to 2.5 parts by weight, more specifically 0.05 part by weight to 2.0 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent. It may be, and more specifically, it may be 0.08 parts by weight to 1.5 parts by weight, but is not limited thereto. If the amount of the curing accelerator is too small, the curing reaction of the epoxy resin may not sufficiently proceed, resulting in deterioration of mechanical and thermal properties. Since this progresses slowly, there may be a problem of increasing the viscosity.

The filler is used for the main purpose of improving the mechanical properties of a cured product by mixing it with an epoxy resin or a curing agent, and generally, mechanical properties are improved when the amount added is increased. Inorganic fillers include extenders such as talc, sand, silica, talc, and calcium carbonate; reinforcing fillers such as mica, quartz, and glass fibers; There are those with special uses such as quartz powder, graphite, alumina, and aerosil (for the purpose of imparting thixotropic properties). Metals include aluminum, aluminum oxide, iron, iron oxide, and copper, which contribute to thermal expansion coefficient, abrasion resistance, thermal conductivity, and adhesion. or antimony oxide (SB ₂ O ₃ ) to impart flame retardancy, barium titanate, organic materials include fillers for weight reduction such as fine plastic spheres (phenolic resin, urea resin, etc.). In addition, various glass fibers or chemical fiber fabrics as fillers having reinforcing properties can be treated as fillers in a broad sense in the manufacture of laminated products. Thixotropic (thixotropic or thixotropic) refers to the property of a liquid state when flowing and a solid state when stationary so that resin impregnated into a laminate or attached to a vertical plane or immersion method does not flow or lose during curing. refers to having), fine particles with a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay is used.

In one embodiment, the filler is not particularly limited, but for example, one selected from the group consisting of glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide, calcium carbonate, or combinations thereof may be used. can The content of the filler in the composition may be 0.01 to 80 parts by weight, or 0.01 to 60 parts by weight, or 0.1 to 50 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

The impact modifier is one of the modifiers used to improve the performance of the material and serves to improve physical properties such as impact strength and processability by being added during the preparation of the epoxy resin composition.

In one embodiment, the impact modifier includes, for example, rubber-based impact modifiers such as carboxyl terminated butadiene acrylonitrile (CTBN) and amine terminated butadiene acrylonitrile (ATBN), poly Ethersulfone, polyetherimide, polycarbonate, polyimide, polyamide, Acrylonitrile butadiene styrene (ABS) and methacrylate butadiene styrene ( Methacrylate butadiene styrene, MBS), or a mixture thereof may be used.

When the impact modifier is included in the epoxy resin composition of the present invention, the content of the impact modifier in the composition may be 2 parts by weight to 95 parts by weight, more specifically 5 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent. It may be part to 90 parts by weight, and more specifically, it may be 10 parts by weight to 88 parts by weight, but is not limited thereto. If the content of the impact modifier is too less than the above level, the toughness of the cured product of the epoxy resin composition may not be sufficient, resulting in deterioration of mechanical and thermal properties. This deteriorates, the curing level of the epoxy resin composition deteriorates, the manufacturing cost of the epoxy resin composition increases, and the viscosity of the epoxy resin composition increases.

The epoxy resin composition of the present invention may further include one or more additive components commonly used in epoxy resin compositions, if necessary.

Such additive components include, for example, an antioxidant, a UV absorber, a resin modifier, a silane coupling agent, a diluent, a colorant, an antifoaming agent, a defoaming agent, a dispersing agent, a viscosity modifier, a gloss modifier, a wetting agent, a conductivity imparting agent, or combinations thereof. It can be used that is selected from.

The antioxidant may be used to further improve the heat resistance stability of the obtained cured product, and is not particularly limited, but examples thereof include phenolic antioxidants (dibutylhydroxytoluene, etc.), sulfur-based antioxidants (mercaptopropionic acid derivatives, etc.) , phosphorus antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) or combinations thereof. The content of the antioxidant in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

Although it does not specifically limit as said UV absorber, For example, the benzotriazole type UV absorber represented by BASF Japan Ltd. TINUBIN P and TINUVIN 234; triazine-based UV absorbers such as TINUVIN 1577ED; A hindered amine-based UV absorber such as CHIMASSOLV 2020FDL or a combination thereof may be used. The content of the UV absorber in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent.

Examples of the resin modifier include, but are not particularly limited to, flexibility imparting agents such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, and urethane prepolymer. The content of the resin modifier in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

The silane coupling agent is not particularly limited, and examples thereof include chloropropyltrimethoxysilane, vinyltrichlorosilane, γmethacryloxypropyltrimethoxysilane, and γaminopropyltriethoxysilane. . The content of the silane coupling agent in the composition may be 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

The diluent is used for the main purpose of reducing the viscosity by adding it to an epoxy resin or curing agent, and when used, it serves to improve flowability, defoaming property, improve penetration into details of parts, or to effectively add fillers. . Diluents generally do not volatilize unlike solvents and remain in the cured product during resin curing, and are divided into reactive and non-reactive diluents. Here, the reactive diluent has one or more epoxy groups and participates in the reaction to form a cross-linked structure in the cured product, and the non-reactive diluent remains only physically mixed and dispersed in the cured product. Commonly used reactive diluents include Butyl Glycidyl Ether (BGE), Phenyl Glycidyl Ether (PGE), and Aliphatic Glycidyl Ether (C12 -C14). , Modified-tert-Carboxylic Glycidyl Ester, etc. Commonly used non-reactive diluents include dibutyl phthalate (DBP), dioctyl phthalate (DOP), nonyl-phenol, hysol, and the like. In one embodiment, the diluent is not particularly limited, but examples include n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene dioxide, diglycidyl aniline, Glycerin triglycidyl ether or one selected from the group consisting of combinations thereof may be used. The content of the diluent in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

A pigment or dye is used as a colorant for adding color to the resin. Commonly used pigments include colorants such as titanium dioxide, cadmium red, channing green, carbon black, chrome green, chrome yellow, navy blue, and channing blue.

In addition, antifoaming and defoaming agents used for the purpose of removing air bubbles in resins, dispersing agents for increasing the dispersion effect of resins and pigments, wetting agents for improving adhesion between epoxy resins and materials, and viscosity modifiers , gloss control agents for adjusting the glossiness of resin, additives for improving adhesion, additives for imparting electrical properties, and the like, various additives can be used.

The method for curing the epoxy resin composition of the present invention is not particularly limited, and conventionally known curing equipment such as a closed curing furnace or a tunnel furnace capable of continuous curing can be used. The heating method used for the curing is not particularly limited, but conventionally known methods such as hot air circulation, infrared heating, or high frequency heating can be used.

The curing temperature and curing time may range from 80° C. to 250° C. for 30 seconds to 10 hours. In one embodiment, after fore-curing at 80°C to 120°C for 0.5 hour to 5 hours, post-curing may be performed at 120°C to 180°C for 0.1 hour to 5 hours. In another embodiment, it may be cured under conditions of 150° C. to 250° C. for 30 seconds to 30 minutes for short-time curing.

In one embodiment, the epoxy resin composition of the present invention is divided into two or more components, for example, a component including a curing agent and a component including an epoxy resin, and stored, and these may be combined before curing. In another specific embodiment, the epoxy resin composition of the present invention may be stored as a thermosetting composition in which each component is blended, and may be used for curing as it is. When stored as a thermosetting composition, it can be stored at low temperature (usually -40°C to 15°C).

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[Example]

<Preparation of anhydrous sugar-alcohol composition containing the first to fifth polyol components>

Preparation Example A1: Preparation of anhydrous sugar alcohol composition using 97% by weight of glucose

A liquid hydrogenated sugar composition having a concentration of 55% by weight (sorbitol 96% by weight, mannitol 0.9% by weight based on solid content) by hydrogenating a glucose product having a purity of 97% in the presence of a nickel catalyst and under a temperature of 125 ° C. and a hydrogen pressure of 60 atm. % and disaccharide or higher polysaccharide alcohol 3.1% by weight) was obtained, which was put into a batch reactor equipped with a stirrer and concentrated by heating at 100 ° C., thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

A reactor was charged with 1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid. Thereafter, the temperature inside the reactor was raised to about 135° C., and a dehydration reaction was performed under a reduced pressure of about 45 mmHg to convert to anhydrous sugar alcohol. After completion of the dehydration reaction, the temperature of the reaction product was cooled to 110° C. or lower, and about 15.7 g of a 50% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less, and concentrated for 1 hour or more under a reduced pressure of 45 mmHg to remove residual moisture and low-boiling substances to obtain about 831 g of anhydrous sugar alcohol conversion solution. As a result of analyzing the obtained anhydrosugar alcohol conversion solution by gas chromatography, the conversion content to isosorbide was 71.9% by weight, and through this, the molar conversion from sorbitol to isosorbide was calculated as 77.6%.

831 g of the obtained anhydrous sugar alcohol conversion solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, distillation was performed at a temperature of 160° C. and a vacuum pressure of 1 mbar, and about 589 g of distillate was obtained (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated therefrom was 95.3%. After separating the distillate, isosorbide (dianhydrosugar alcohol) [second polyol component] 11.5% by weight, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4% by weight, sorbitan (anhydrous sugar alcohol) 0.4% by weight alcohol) [first polyol component] 7.4% by weight, polysaccharide alcohol represented by Formula 1 [third polyol component] and anhydrosugar alcohol derived therefrom (ie, formed by removing water molecules from polysaccharide alcohol) [agent 4 polyol component] and 78.2% by weight of their polymer [fifth polyol component], the number average molecular weight of the composition is 208 g / mol, the polydispersity index of the composition is 1.25, the composition About 242 g of an anhydrous sugar alcohol composition having a hydroxyl value of 751 mg KOH/g and an average number of -OH groups per molecule of 2.78 in the composition was obtained.

<Preparation of anhydrous sugar alcohol-alkylene glycol composition>

Preparation Example B1: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 300 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

100 parts by weight (100 g) of the anhydrous sugar alcohol composition obtained in Preparation Example A1 and 1.0 g of KOH were put into a pressurized reactor, and the process of pressurizing and evacuating with nitrogen gas was repeated three times. Thereafter, the internal temperature of the reactor was raised to 100° C. to remove moisture, and after all moisture was removed, 300 parts by weight (300 g) of propylene oxide was slowly added while performing an addition reaction at 100° C. to 140° C. Then, 4 g of metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and stirring was performed for 1 hour to 5 hours while maintaining the internal temperature of the reactor at 100 ° C to 120 ° C. After monitoring the residual metal content, the metal When completely removed and not detected, the temperature inside the reactor was cooled to 60°C to 90°C, followed by filtration. By purifying the filtrate using a mixed ion exchange resin, 350 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

<Preparation of end-capped isocyanate prepolymer composition>

Example A1: OH equivalent of polyether polyol (0.8 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.2 equivalent of OH) is 4, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

4.3 g of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1 (0.2 equivalent of OH), 80 g of polypropylene glycol (0.8 equivalent of OH), 18.9 g of isophorone diisocyanate (1.7 equivalent of NCO) and di-n as a catalyst - 0.5 g of dibutyltin dilaurate (DBTDL) was put into the reactor, and the internal temperature of the reactor was slowly raised to reach 80° C., followed by stirring for 3 hours to proceed with the urethane reaction. After completion of the reaction, the temperature inside the reactor was adjusted to 60°C. After measuring the NCO content of the reaction product, 1.4 equivalents of t-butyl phenol relative to 1 equivalent of NCO was introduced into the reactor as an end-capping agent, and the end-capping reaction proceeded while mixing them. At this time, the reaction was terminated when the NCO content became 0% while monitoring the NCO content. After completion of the reaction, the final reaction product was cooled to room temperature to obtain 100 g of an end-capped isocyanate prepolymer composition.

Example A2: OH equivalent of polyether polyol (0.7 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.3 equivalent of OH) is 2.33, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 6.4 g (OH 0.3 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 90 g of an isocyanate prepolymer composition end-capped in the same manner as in Example A1, except that 70 g (0.7 equivalent of OH) was used and 1.4 equivalent of allyl phenol was used instead of t-butyl phenol as the end capping agent. was obtained.

Example A3: OH equivalent of polyether polyol (0.7 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.3 equivalent of OH) is 2.33, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 6.4 g (OH 0.3 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 90 g of an end-capped isocyanate prepolymer composition was obtained by following the same method as in Example A1, except for changing to 70 g (0.7 equivalent of OH).

Example A4: OH equivalent of polyether polyol (0.7 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.3 equivalent of OH) is 2.33, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.6

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 6.4 g (OH 0.3 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 70 g (OH 0.7 equivalent), and the content of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 17.7 g (NCO 1.6 equivalent). - Obtained 90 g of a capped isocyanate prepolymer composition.

Example A5: OH equivalent of polyether polyol (0.7 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.3 equivalent of OH) is 2.33, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.9

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 6.4 g (OH 0.3 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 70 g (OH 0.7 equivalent), and the amount of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 21.1 g (NCO 1.9 equivalent). - Obtained 90 g of a capped isocyanate prepolymer composition.

Example A6: OH equivalent of polyether polyol (0.5 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.5 equivalent of OH) is 1, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 16.1 g (OH 0.5 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 75 g (OH 0.5 equivalent), and the content of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 28.3 g (NCO 1.7 equivalent). - Obtained 100 g of the capped isocyanate prepolymer composition.

Example A7: OH equivalent of polyether polyol (0.3 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.7 equivalent of OH) is 0.43, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 22.6 g (OH 0.7 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 45 g (OH 0.3 equivalent), and the content of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 28.3 g (NCO 1.7 equivalent). - Obtained 90 g of a capped isocyanate prepolymer composition.

Comparative Example A1: OH equivalent of polyether polyol (0.7 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.3 equivalent of OH) is 2.33, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.5

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 7.7 g (OH 0.3 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 84 g (OH 0.7 equivalent), and the content of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 20.0 g (NCO 1.5 equivalent). - Obtained 100 g of the capped isocyanate prepolymer composition.

Comparative Example A2: OH equivalent of polyether polyol (0.7 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.3 equivalent of OH) is 2.33, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 2.0

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 7.7 g (OH 0.3 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 84 g (OH 0.7 equivalent), and the content of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 26.6 g (NCO 2.0 equivalent). - Obtained 100 g of the capped isocyanate prepolymer composition.

Comparative Example A3: OH equivalent (OH 0.9 equivalent) of polyether polyol / OH equivalent (OH 0.1 equivalent) of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 is 9.0, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 2.1 g (OH 0.1 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 100 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example A1 except for changing to 90 g (0.9 equivalent of OH).

Comparative Example A4: OH equivalent of polyether polyol (0.2 equivalent of OH) / OH equivalent of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 (0.8 equivalent of OH) is 0.25, total NCO equivalent of polyisocyanate / polyol composition Preparation of an end-capped isocyanate prepolymer composition with a total OH equivalent weight of 1.7

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 4.3 g (OH 0.2 equivalent) to 34.5 g (OH 0.8 equivalent), and the content of polypropylene glycol was changed from 80 g (OH 0.8 equivalent) to 40 g (OH 0.2 equivalent), and the content of isophorone diisocyanate was changed from 18.9 g (NCO 1.7 equivalent) to 37.8 g (NCO 1.7 equivalent). - Obtained 100 g of the capped isocyanate prepolymer composition.

The compositions and weight average molecular weights of the end-capped isocyanate prepolymer compositions obtained in Examples A1 to A7 and Comparative Examples A1 to A4 are shown in Table 1 below.

<Evaluation of physical properties of end-capped isocyanate prepolymer composition>

1. Weight average molecular weight (Mw: unit g/mol)

The weight average molecular weight of the end-capped isocyanate prepolymer compositions obtained in Examples A1 to A7 and Comparative Examples A1 to A4 was measured using an Agilent 1260 Infinity instrument. At this time, tetrahydrofuran (THF) was used as the solvent, and the measured concentration was adjusted to 1% by weight.

<Preparation of Epoxy Resin Composition>

Example B1: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A3 as an adhesion promoter and a bio-based epoxy resin as an epoxy resin

As an adhesion promoter for epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A3, diglycidyl ether isosorbide (DGEI) derived from biomass as an epoxy resin, Jeil Chemical Co., Ltd. )) 3.0g, 0.45g of curing agent for epoxy resin (dicyandiamide (DICY), Evonik Co., Ltd., Dicyanex 1400F) for inducing curing reaction at high temperature and stable at room temperature, and curing accelerator for epoxy resin (urea derivative (DIURON)) , Evonik Company (manufactured by), Amicure UR-D) 0.05 g, calcium carbonate having a particle size of 21 to 33 μm as a filler (CaCO ₃ , OMYA Company (manufactured), OMYACARB 30-CN) 1.0 g and a core as an impact modifier - An epoxy resin composition was prepared by putting 3.0 g of shell rubber (KANEKA Co., Ltd., MX-154) in a paste mixer and mixing for 6 minutes.

Example B2: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A3 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

Same as Example B1, except that 1.0 g of biomass-derived DGEI and 2.0 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) of bisphenol A were used as the epoxy resin. An epoxy resin composition was prepared by the method.

Example B3: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A3 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as an epoxy resin

Same as Example B1, except that 1.5 g of biomass-derived DGEI and 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) of bisphenol A were used as the epoxy resin. An epoxy resin composition was prepared by the method.

Example B4: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A3 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

Same as Example B1, except that 2.0 g of biomass-derived DGEI and 1.0 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) of bisphenol A were used as the epoxy resin. An epoxy resin composition was prepared by the method.

Example B5: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A1 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A1 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Example B6: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A2 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A2 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin. An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Example B7: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A4 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A4 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Example B8: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A5 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A5 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Example B9: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A6 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A6 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin. An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Example B10: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A7 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Example A7 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin. An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Example B11: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Example A3 as an adhesion promoter and a petroleum-based epoxy resin as an epoxy resin

Same as Example B1, except that 3.0 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) of bisphenol A was used instead of biomass-derived DGEI as the epoxy resin. An epoxy resin composition was prepared by the method.

Comparative Example B1: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Comparative Example A1 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Comparative Example A1 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Comparative Example B2: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Comparative Example A2 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Comparative Example A2 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of biomass-derived DGEI and bisphenol A were used as the epoxy resin. An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Comparative Example B3: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Comparative Example A3 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for the epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Comparative Example A3 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

Comparative Example B4: Preparation of an epoxy resin composition using the end-capped isocyanate prepolymer composition of Comparative Example A4 as an adhesion promoter and a bio-based epoxy resin and a petroleum-based epoxy resin as epoxy resins

As an adhesion promoter for epoxy resin, 2.5 g of the end-capped isocyanate prepolymer composition of Comparative Example A4 was used instead of the end-capped isocyanate prepolymer composition of Example A3, and 1.5 g of DGEI derived from biomass and bisphenol A as the epoxy resin An epoxy resin composition was prepared in the same manner as in Example B1, except that 1.5 g of diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) was used.

The compositions of the epoxy resin compositions obtained in Examples B1 to B11 and Comparative Examples B1 to B4 are shown in Table 2 below.

<Evaluation of physical properties of epoxy resin composition>

Using the epoxy resin compositions prepared in Examples B1 to B11 and Comparative Examples B1 to B4 as adhesives, physical properties were measured in the following manner, and the results are shown in Table 3 below.

(1) Evaluation of T-peel strength (unit: N/25 mm)

T-peel strength was measured as follows based on the ASTM D-1876 standard.

A cold-rolled steel sheet having a length of 150 mm × width 25 mm × thickness of 1 mm was bent at a right angle, and at this time, the lengths of each side were 70 mm and 80 mm after bending. Each of the epoxy resin compositions obtained in Examples B1 to B11 and Comparative Examples B1 to B4 was applied as an adhesive to a surface having a length of 80 mm × a width of 25 mm, and then a small amount of microbeads were laminated thereon to maintain a constant adhesive thickness. . After that, another cold-rolled steel sheet was covered and fixed thereon, and cured at 180° C. for 30 minutes. After curing, the T-peel strength was measured using a universal tester for the adhesive specimen cooled to 23 ° C. At this time, the measurement of the T-peel strength was performed while applying a load in the direction of 180 degrees at a tensile rate of 50 mm/min. At this time, the T-peel strength of each specimen was measured 5 times and the average value was calculated.

(2) Evaluation of room temperature impact strength (unit: N/mm)

The impact strength at room temperature was measured according to the ISO 11343 standard as follows.

A steel specimen with a size of 90 mm in length x 20 mm in width x 1 mm in thickness, with a 30 mm distal end used as an adhesive surface and a tuning fork-shaped non-bonded end portion, was used. After each of the epoxy resin compositions obtained in Examples B1 to B11 and Comparative Examples B1 to B4 were applied to the adhesive surface of the 30 mm end, a small amount of microbeads were laminated thereon to maintain a constant adhesive thickness. After that, another steel specimen was covered and fixed thereon, and cured at 180° C. for 30 minutes. After curing, impact strength at room temperature was measured on the adhesive specimen cooled to room temperature using a drop impact tester. At this time, the measurement of impact strength at room temperature was tested so that the wedge jig passed through the adhesive part of the adhesive part, and the impact speed was carried out at 2 m / s to 3 m / s. At this time, the room temperature impact strength for each specimen was measured 5 times and the average value was calculated.

As shown in Table 3, in the case of the epoxy resin compositions of Examples B1 to B11 containing the end-capped isocyanate prepolymer composition according to the present invention as an adhesion promoter, all have T-peel strengths of 309 N / 25 mm or more, The room temperature impact strength was over 35 N/mm, and it exhibited excellent adhesiveness and impact resistance.

That is, when the end-capped isocyanate prepolymer composition according to the present invention is used as an adhesion promoter for epoxy resins, a biomass-derived epoxy resin alone is used as well as when a conventional petroleum-based epoxy resin is used as the epoxy resin. , Even when a biomass-derived epoxy resin and a conventional petroleum-based epoxy resin are mixed and used, excellent adhesiveness and impact resistance can be exhibited.

On the other hand, in the case of the epoxy resin compositions of Comparative Examples B1 and B2, surface peeling (a phenomenon in which peeling occurs at the interface between an object to be adhered and the adhesive) or material peeling (a phenomenon in which peeling or cracks occur inside the adhesive) occurs, thereby improving adhesive properties. This was poor, and the room temperature impact strength was also lowered, resulting in poor impact resistance. In the case of the epoxy resin composition of Comparative Example B3, the soft portion in the end-capped isocyanate prepolymer composition was excessively expressed, so the viscosity was very low, resulting in surface peeling, resulting in poor adhesion, and poor impact resistance due to low impact strength at room temperature. In the case of the epoxy resin composition of Comparative Example B4, the molecular weight of the end-capped isocyanate prepolymer composition was too high, and the viscosity was very high, resulting in material exfoliation and poor adhesion, and room temperature impact strength was also lowered, resulting in poor impact resistance. .

As such, when the end-capped isocyanate prepolymer composition according to the present invention is used as an adhesion promoter for epoxy resins, not only when conventional petroleum-based epoxy resins are used as epoxy resins, but also when biomass-derived epoxy resins are used. Since the epoxy resin composition can exhibit excellent adhesiveness and impact resistance, the epoxy resin composition according to the present invention can be utilized as an environmentally friendly adhesive.

Claims (17)

As an end-capped isocyanate prepolymer composition,
It is prepared by reacting an isocyanate prepolymer composition and an end capping agent,
The isocyanate prepolymer composition is prepared by urethane reaction of a polyol composition and polyisocyanate including an anhydrous sugar alcohol-alkylene glycol composition and polyether polyol,
The anhydrous sugar alcohol-alkylene glycol composition is prepared by an addition reaction of anhydrosugar alcohol composition and alkylene oxide,
The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is represented by the formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is the first to fourth polyol components At least one polymer selected from
The ratio of OH equivalents of the polyether polyol to OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition (OH equivalents of polyether polyol / OH equivalents of anhydrous sugar alcohol-alkylene glycol composition) is greater than 0.25 and less than 9, ,
Total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) are greater than 1.5 and less than 2.0;
End-capped isocyanate prepolymer composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. According to claim 1,
the first polyol component is monohydrosugar hexitol;
the second polyol component is dianhydrosugar hexitol;
The fourth polyol component is selected from a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof,
End-capped isocyanate prepolymer composition:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
n is each independently an integer of 0 to 4; The end-capped isocyanate prepolymer composition according to claim 1, wherein the fifth polyol component comprises at least one selected from the group consisting of condensation polymers prepared from the following polycondensation reaction:
- polycondensation reaction of the first polyol component,
- polycondensation reaction of the second polyol component,
- polycondensation reaction of the third polyol component,
- polycondensation reaction of the fourth polyol component,
- polycondensation reaction between the first polyol component and the second polyol component;
- polycondensation reaction between the first polyol component and the third polyol component;
- polycondensation reaction between the first polyol component and the fourth polyol component;
- polycondensation reaction between the second polyol component and the third polyol component;
- polycondensation reaction between the second polyol component and the fourth polyol component;
- polycondensation reaction between the third polyol component and the fourth polyol component;
- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component,
- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component,
- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component,
- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or
- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component. The end-capped isocyanate prepolymer composition according to claim 1, wherein the anhydrosugar alcohol composition satisfies the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrous sugar alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrous sugar alcohol composition is 2.54 to 21.36. The method of claim 1, wherein the anhydrous sugar alcohol composition hydrogenates a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, heats the obtained hydrogenated sugar composition under an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product An end-capped isocyanate prepolymer composition prepared by thin film distillation. The end-capped isocyanate prepolymer composition according to claim 5, wherein the glucose-containing saccharide composition contains 41% to 99.5% by weight of glucose based on the total weight of the saccharide composition. The end-capped isocyanate prepolymer composition according to claim 1, wherein the anhydrous sugar alcohol-alkylene glycol composition is prepared by adding 100 parts by weight to 500 parts by weight of an alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition. The end-capped isocyanate prepolymer composition of claim 1 , wherein the polyether polyol comprises a polyalkylene glycol. The method of claim 1, wherein the end-capping agent is at least one selected from the group consisting of phenol-based compounds, triazine-based compounds, alcohol compounds, amine compounds, benzene-based compounds, dicarboxylic acid ester-based compounds, novolac-based compounds, and combinations thereof. , End-capped isocyanate prepolymer composition. The end-capped isocyanate prepolymer composition according to claim 1, wherein the weight average molecular weight of the end-capped isocyanate prepolymer composition is from 7,951 to 26,499 g/mol. As a method for preparing an end-capped isocyanate prepolymer composition,
(1) preparing an isocyanate prepolymer composition by urethane-reacting a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and polyether polyol with polyisocyanate; and
(2) reacting the isocyanate prepolymer composition obtained in step (1) with an end capping agent;
The anhydrous sugar alcohol-alkylene glycol composition is prepared by an addition reaction of anhydrosugar alcohol composition and alkylene oxide,
The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is represented by the formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is the first to fourth polyol components At least one polymer selected from
The ratio of OH equivalents of the polyether polyol to OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition (OH equivalents of polyether polyol / OH equivalents of anhydrous sugar alcohol-alkylene glycol composition) is greater than 0.25 and less than 9, ,
Total NCO equivalents of the polyisocyanate/total OH equivalents of the polyol composition (total NCO equivalents/total OH equivalents) are greater than 1.5 and less than 2.0;
Process for preparing the end-capped isocyanate prepolymer composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. An adhesion promoter for epoxy resin comprising the end-capped isocyanate prepolymer composition according to any one of claims 1 to 10. The adhesion promoter for the epoxy resin of claim 12; And an epoxy resin; containing, an epoxy resin composition. 14. The method of claim 13, wherein the epoxy resin is bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolak type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-dicyclic epoxy resin, glycy An epoxy resin composition selected from the group consisting of dill ester-type epoxy resins, brominated epoxy resins, biomass-derived epoxy resins, epoxidized soybean oil, or combinations thereof. The epoxy resin composition according to claim 13, further comprising one or more selected from a curing agent, a curing accelerator, a filler, an impact modifier, or a combination thereof. 14. The method of claim 13, selected from the group consisting of an antioxidant, a UV absorber, a resin modifier, a silane coupling agent, a diluent, a colorant, an antifoaming agent, a defoaming agent, a dispersing agent, a viscosity modifier, a gloss modifier, a wetting agent, a conductivity imparting agent, or a combination thereof. The epoxy resin composition further comprising an additive to be. An adhesive comprising the epoxy resin composition of claim 13.