KR102675946B1 - Anaerobic adhesive composition with excellent oil resistance and impact resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to an anaerobic adhesive composition and a method for producing the same, and more specifically, includes a (meth)acrylic-modified polyurethane component, a (meth)acrylic-modified epoxy component, a (meth)acrylic monomer, and an anaerobic curing component. It relates to an anaerobic adhesive composition that can be cured at room temperature without separate heat or ultraviolet irradiation, has excellent adhesion to metal, and has excellent oil resistance and impact resistance, and a method for manufacturing the same.

Description

Anaerobic adhesive composition with excellent oil resistance and impact resistance and method for preparing the same}

The present invention relates to an anaerobic adhesive composition and a method for producing the same, and more specifically, includes a (meth)acrylic-modified polyurethane component, a (meth)acrylic-modified epoxy component, a (meth)acrylic monomer, and an anaerobic curing component. It relates to an anaerobic adhesive composition that can be cured at room temperature without separate heat or ultraviolet irradiation, has excellent adhesion to metal, and has excellent oil resistance and impact resistance, and a method for manufacturing the same.

A variety of adhesive compositions have been developed for adhesion between metal materials and non-metal materials (eg, organic materials such as plastic materials) or between metals.

For example, Republic of Korea Patent Publication No. 10-2018-0128444 discloses an anaerobic curable (meth)acrylate composition with excellent tensile strength performance and a method for producing the same, but does not disclose the oil resistance of the composition at all.

Meanwhile, Korean Patent Publication No. 10-2022-0007608 discloses hydroxyalkyl (meth)acrylates having an alkyl group containing 2 to 4 carbons, short alkyl (meth)acrylates having an alkyl group containing 6 or less carbons, etc. An oil-resistant adhesive composition containing a latent adhesive and a photoinitiator has been disclosed, but this composition has a problem of poor workability in processes where ultraviolet irradiation is not easy, such as thread locker and gasket sealant applications.

Meanwhile, Korean Patent Publication No. 10-2017-0125328 discloses manufacturing an intermetallic conductive adhesive using acrylic-modified polyurethane, other acrylic monomers, and a thermal polymerization initiator. However, adhesive compositions prepared in this way lack oil resistance, and adhesion needs to be further improved.

In addition, Korean Patent Publication No. 10-2022-0117937 discloses a coating composition containing (meth)acrylic modified polyurethane, (meth)acrylic monomer, and epoxy resin, and curing through a radical polymerization mechanism upon heat initiation. The composition can provide a coating with excellent adhesion to metal and improved oil resistance. However, the composition requires high temperature curing because it uses a radical thermal polymerization initiator. While (meth)acrylic monomer and (meth)acrylic-modified polyurethane are cured by a radical thermal polymerization initiator, epoxy resins have different curing mechanisms. requires a separate epoxy curing accelerator.

Accordingly, there is a need for the development of improved adhesive compositions that can solve the problems of the above-described prior technologies.

The purpose of the present invention is to provide an adhesive composition that can be cured at room temperature and has significantly improved oil resistance and impact resistance while maintaining excellent adhesive strength and a method for producing the same.

One aspect of the present invention is a (meth)acrylic-modified polyurethane component comprising a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; A (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Epoxy component; (meth)acrylic monomer; and an anaerobic curing component; wherein, based on a total of 100 parts by weight of the composition, the content of the (meth)acrylic-modified polyurethane component is greater than 18 parts by weight and less than 65 parts by weight; The content of the (meth)acrylic-modified epoxy component is greater than 12 parts by weight and less than 45 parts by weight; The (meth)acrylic monomer content is greater than 7 parts by weight and less than 50 parts by weight; Consists of the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. An anaerobic adhesive composition is provided, wherein the total content of those selected from the group is greater than 10 parts by weight and less than 70 parts by weight.

Another aspect of the present invention is a (meth)acrylic-modified polyurethane component comprising a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; A (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Epoxy component; (meth)acrylic monomer; and an anaerobic curing component; wherein the content of the (meth)acrylic-modified polyurethane component is greater than 18 parts by weight and less than 65 parts by weight in a total of 100 parts by weight of the mixture; The content of the (meth)acrylic-modified epoxy component is greater than 12 parts by weight and less than 45 parts by weight; The (meth)acrylic monomer content is greater than 7 parts by weight and less than 50 parts by weight; Consists of the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. A method for producing an anaerobic adhesive composition is provided, characterized in that the total content of those selected from the group is greater than 10 parts by weight and less than 70 parts by weight.

Another aspect of the present invention provides an article to which the anaerobic adhesive composition of the present invention is applied.

The anaerobic adhesive composition of the present invention can be cured at room temperature without separate heat or ultraviolet irradiation, has excellent adhesion to metal, and exhibits excellent oil resistance and impact resistance.

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

As used herein, the term “(meth)acrylic” includes acrylic, methacrylic, or a combination thereof, and the term “(meth)acrylate” includes acrylate, methacrylate, or a combination thereof.

The anaerobic adhesive composition of the present invention includes a (meth)acrylic-modified polyurethane component including hydrophilic (meth)acrylic-modified polyurethane and lipophilic (meth)acrylic-modified polyurethane; A (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Epoxy component; (meth)acrylic monomer; and an anaerobic curing component; wherein, based on a total of 100 parts by weight of the composition, the content of the (meth)acrylic-modified polyurethane component is greater than 18 parts by weight and less than 65 parts by weight; The content of the (meth)acrylic-modified epoxy component is greater than 12 parts by weight and less than 45 parts by weight; The (meth)acrylic monomer content is greater than 7 parts by weight and less than 50 parts by weight; Consists of the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. The total content of those selected from the group is more than 10 parts by weight and less than 70 parts by weight.

If the content of the (meth)acrylic-modified polyurethane component in a total of 100 parts by weight of the composition of the present invention is 18 parts by weight or less, the oil resistance of the composition decreases and the impact resistance at room temperature becomes very poor. Conversely, if the content is 65 parts by weight or more. The room temperature adhesiveness of the backing composition becomes very poor, and the room temperature impact resistance decreases. In one embodiment, the content of the (meth)acrylic-modified polyurethane component in a total of 100 parts by weight of the composition is greater than 18 parts by weight, 18.1 parts by weight or more, 18.5 parts by weight or more, 19 parts by weight or more, 19.5 parts by weight or more, or 20 parts by weight. It may be more than 65 parts by weight, less than 64.9 parts by weight, less than 64 parts by weight, less than 63 parts by weight, less than 62 parts by weight, less than 61 parts by weight, or less than 60 parts by weight, but is not limited thereto.

If the content of the (meth)acrylic-modified epoxy component in a total of 100 parts by weight of the composition of the present invention is 12 parts by weight or less, the room temperature adhesiveness and oil resistance of the composition are very poor, and on the contrary, if the content is more than 45 parts by weight, the composition has a Impact resistance becomes very poor. In one embodiment, the content of the (meth)acrylic-modified epoxy component in a total of 100 parts by weight of the composition is greater than 12 parts by weight, 12.1 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight. parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, and also less than 45 parts by weight, 44.9 parts by weight or less, 44 parts by weight or less, 43 parts by weight or less, 42 parts by weight or less. , may be 41 parts by weight or less or 40 parts by weight or less, but is not limited thereto.

If the content of the (meth)acrylic monomer in the total 100 parts by weight of the composition of the present invention is 7 parts by weight or less, the room temperature adhesiveness of the composition becomes very poor, and on the contrary, if the content is more than 50 parts by weight, the oil resistance and room temperature impact resistance of the composition are poor. It becomes. In one embodiment, the (meth)acrylic monomer content in a total of 100 parts by weight of the composition is greater than 7 parts by weight, 7.1 parts by weight or more, 7.5 parts by weight or more, 8 parts by weight or more, 8.5 parts by weight or more, 9 parts by weight or more, It may be 9.5 parts by weight or more or 10 parts by weight or more, and also less than 50 parts by weight, 49.9 parts by weight or less, 49 parts by weight or less, 48 parts by weight or less, 47 parts by weight or less, 46 parts by weight or less, 45 parts by weight or less, 44 parts by weight. It may be 43 parts by weight or less, 43 parts by weight or less, 42 parts by weight or less, 41 parts by weight or less, or 40 parts by weight or less, but is not limited thereto.

The hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, and the (meth)acrylic-derived from anhydrosugar alcohol-alkylene oxide adduct in a total of 100 parts by weight of the composition of the present invention. If the total content of the modified epoxy compound or a combination thereof is 10 parts by weight or less, the oil resistance of the composition deteriorates. Conversely, if the content is 70 parts by weight or more, the adhesiveness and room temperature impact resistance of the composition deteriorate. . In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, and the anhydrosugar alcohol-alkylene oxide adduct derived (meth) in a total of 100 parts by weight of the composition. The total content selected from the group consisting of an acrylic-modified epoxy compound or a combination thereof will be more than 10 parts by weight, 10.1 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, or 14 parts by weight or more. It can also be less than 70 parts by weight, 69.9 parts by weight or less, 69 parts by weight or less, 68 parts by weight or less, 67 parts by weight or less, 66 parts by weight or less, 65 parts by weight or less, 64 parts by weight or less, 63 parts by weight or less, 62 parts by weight or less. It may be less than or equal to 61 parts by weight, or less than or equal to 60 parts by weight, but is not limited thereto.

In one embodiment, in a total of 100 parts by weight of the composition of the present invention, the anaerobic curing component may be included in an amount of, for example, 0.5 parts by weight to 15 parts by weight, more specifically, 0.5 parts by weight or more, 1 part by weight. or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, or 3 parts by weight or more, and also 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, or 11 parts by weight or less. It may be included in an amount of 10 parts by weight or less, but is not limited thereto.

Hereinafter, the components included or capable of being included in the anaerobic adhesive composition of the present invention will be described in more detail.

[(meth)acrylic-modified polyurethane component]

The (meth)acrylic-modified polyurethane component included in the composition of the present invention includes hydrophilic (meth)acrylic-modified polyurethane and lipophilic (meth)acrylic-modified polyurethane.

In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane includes polymerized units derived from anhydrosugar alcohol-alkylene oxide adduct; polymerized units derived from polyisocyanates; and a polymerized unit derived from hydroxyalkyl (meth)acrylate.

In one embodiment, the lipophilic (meth)acrylic-modified polyurethane includes polymerized units derived from a lipophilic polyol; polymerized units derived from polyisocyanates; and a polymerized unit derived from hydroxyalkyl (meth)acrylate.

In one embodiment, the (meth)acrylic-modified polyurethane component is 16 to 84 parts by weight of the hydrophilic (meth)acrylic-modified polyurethane and the above, based on a total of 100 parts by weight of the (meth)acrylic-modified polyurethane component. It may contain 16 to 84 parts by weight of lipophilic (meth)acrylic-modified polyurethane. More specifically, in a total of 100 parts by weight of the (meth)acrylic-modified polyurethane component, the hydrophilic and lipophilic (meth)acrylic-modified polyurethane are contained in an amount of 16 parts by weight or more, 17 parts by weight or more, and 18 parts by weight or more, respectively. , may be included in an amount of 19 parts by weight or more or 20 parts by weight or more, and the hydrophilic and lipophilic (meth)acrylic-modified polyurethane is contained in an amount of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, and 81 parts by weight, respectively. It may be included in an amount of less than or equal to 80 parts by weight, but is not limited thereto.

In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane may be represented by the following formula (1):

[Formula 1]

In Formula 1,

Each R1 is independently an alkylene group, specifically a C2-C8 linear or C3-C8 branched alkylene group, and more specifically a C2-C6 linear or C3-C6 branched alkylene group,

R2 is each independently an alkylene group, a cycloalkylene group, or an arylene group, and specifically, a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group,

Each R3 is independently an alkylene group, specifically a C1-C8 linear or C3-C8 branched alkylene group, and more specifically a C2-C6 linear or C3-C6 branched alkylene group,

R4 is each independently a hydrogen atom or an alkyl group, and specifically, a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group,

M is a divalent organic group derived from anhydrosugar alcohol, specifically, a divalent organic group derived from dianhydrosugar hexitol, and more specifically, a divalent organic group derived from isosorbide, isomannide, or isoidide. It is a device, and more specifically, is selected from the following formulas,

m and n each independently represent an integer from 0 to 15,

m+n is an integer from 1 to 30, more specifically an integer from 1 to 25, even more specifically an integer from 1 to 20, even more specifically an integer from 3 to 15, even more specifically an integer from 5 to 15 represents the integer of .

In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane may include, but is not limited to, one or more selected from the group consisting of compounds represented by the following formulas:

In the above formulas,

m and n each independently represent an integer from 0 to 15,

m+n is an integer from 1 to 30, more specifically an integer from 1 to 25, even more specifically an integer from 1 to 20, even more specifically an integer from 3 to 15, even more specifically an integer from 5 to 15 represents the integer of .

The hydrophilic (meth)acrylic-modified polyurethane can be obtained by reacting polyisocyanate with an anhydrosugar alcohol-alkylene oxide adduct and then reacting hydroxyalkyl (meth)acrylate.

More specifically, the hydrophilic (meth)acrylic-modified polyurethane is prepared by: (a) reacting anhydrosugar alcohol-alkylene oxide adduct with polyisocyanate to prepare an intermediate having an isocyanate end; and (b) reacting the intermediate obtained in step (a) with hydroxyalkyl (meth)acrylate.

According to one embodiment, an intermediate having an isocyanate end is prepared by reacting 2 equivalents of diisocyanate with 1 equivalent of anhydrosugar alcohol (e.g., isosorbide (ISB))-alkylene oxide adduct, and then the isocyanate end of the intermediate is reacted with 2 equivalents of diisocyanate. Hydrophilic (meth)acrylic-modified polyurethane can be prepared by reacting with 2 equivalents of hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate).

According to one embodiment, the reaction of the anhydrosugar alcohol-alkylene oxide adduct with the polyisocyanate is carried out at room temperature, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)). It may be performed at an elevated temperature (eg, 50 to 100°C, preferably 50 to 70°C) for an appropriate time (eg, 0.1 to 5 hours, preferably 0.5 to 2 hours).

According to one embodiment, the reaction between the reaction product of the anhydrosugar alcohol-alkylene oxide adduct and polyisocyanate (i.e., the intermediate obtained from step (a)) and hydroxyalkyl (meth)acrylate is optionally carried out using a catalyst ( In the presence of a tin-based catalyst, such as dibutyltin dilaurate (DBTDL), at elevated temperature (e.g., 50 to 100° C., preferably 50 to 70° C.) for an appropriate time (e.g., 0.1 to 5 hours, preferably). It may be performed for 0.5 to 2 hours.

In one embodiment, the lipophilic polyol is a polyol having low surface energy characteristics, and may be specifically selected from polytetramethylene glycol, polypropylene glycol, polyethylene glycol, or a combination thereof, but is not limited thereto. .

In one embodiment, the number average molecular weight (Mn) of the lipophilic polyol is not particularly limited, but is specifically 200 to 3,000 g/mol, more specifically 500 to 2,500 g/mol, and even more specifically 700 to 3,000 g/mol. It may be 2,300 g/mol, more specifically 1,000 to 2,000 g/mol.

In one embodiment, the lipophilic (meth)acrylic-modified polyurethane may be represented by the following formula (2):

[Formula 2]

In Formula 2,

R1 is each independently an alkylene group, a cycloalkylene group, or an arylene group,

R2 is each independently an alkylene group,

R3 is each independently a hydrogen atom or an alkyl group,

L is a divalent organic group derived from a lipophilic polyol,

The number average molecular weight of the lipophilic polyol is 200 to 3,000 g/mol.

More specifically, in Formula 2 above,

R1 is each independently a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group,

R2 is each independently a C1-C8 linear or C3-C8 branched alkylene group,

R3 is each independently a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group,

L is a divalent organic group derived from a lipophilic polyol selected from polytetramethylene glycol, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or combinations thereof,

The number average molecular weight of the lipophilic polyol is 500 to 2,500 g/mol.

The lipophilic (meth)acrylic-modified polyurethane can be obtained by reacting polyisocyanate with lipophilic polyol and then reacting hydroxyalkyl (meth)acrylate.

More specifically, the lipophilic (meth)acrylic-modified polyurethane includes the steps of (c) reacting a lipophilic polyol and polyisocyanate to prepare an intermediate having an isocyanate end; and (d) reacting the intermediate obtained in step (c) with hydroxyalkyl (meth)acrylate.

According to one embodiment, 2 equivalents of diisocyanate are reacted with 1 equivalent of a lipophilic polyol (e.g., polytetramethylene glycol, polypropylene glycol, or polydimethylsiloxane polyol with a number average molecular weight of 200 to 3,000 g/mol) to form an isocyanate terminal. After preparing an intermediate having, the isocyanate terminal of the intermediate is reacted with 2 equivalents of hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate) to produce lipophilic (meth)acrylic-modified polyurethane. It can be manufactured.

According to one embodiment, the reaction of the lipophilic polyol and polyisocyanate is carried out at room temperature or at elevated temperature (e.g., 50 °C), optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)). It may be performed at a temperature ranging from 100°C to 100°C, preferably 50 to 70°C, for an appropriate time (eg, 0.1 to 5 hours, preferably 0.5 to 2 hours).

According to one embodiment, the reaction between the reaction product of the lipophilic polyol and polyisocyanate (i.e., the intermediate obtained from step (c)) and hydroxyalkyl (meth)acrylate is optionally performed using a catalyst (e.g., dibutyltin In the presence of a tin-based catalyst such as laurate (DBTDL), at elevated temperature (e.g., 50 to 100° C., preferably 50 to 70° C.) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours). time) can be performed.

(meth)acrylic-modified polyurethane component manufacturing method

In one embodiment, the (meth)acrylic-modified polyurethane component is (1) an intermediate having an isocyanate terminal by reacting a polyol component including an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol with polyisocyanate. manufacturing step; and (2) reacting the intermediate obtained in step (1) with hydroxyalkyl (meth)acrylate.

In another embodiment, the (meth)acrylic-modified polyurethane component is prepared by a method comprising mixing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane (second manufacturing method) ), and more specifically, (i) polymerized units derived from anhydrosugar alcohol-alkylene oxide adduct; polymerized units derived from polyisocyanates; and a polymerized unit derived from a hydroxyalkyl (meth)acrylate; a hydrophilic (meth)acrylic-modified polyurethane comprising and (ii) a polymerized unit derived from a lipophilic polyol; polymerized units derived from polyisocyanates; and a polymerization unit derived from hydroxyalkyl (meth)acrylate.

According to one embodiment, in the first method of producing the (meth)acrylic-modified polyurethane component, the polyol component is anhydrosugar alcohol-alkylene oxide adduct 16 to 84, based on 100 parts by weight of the total polyol component. It may include 16 to 84 parts by weight of a lipophilic polyol, and more specifically, in the total 100 parts by weight of the polyol component, an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol are each included in an amount of 16 parts by weight or more, It may be included in an amount of 17 parts by weight or more, 18 parts by weight, 19 parts by weight or more, or 20 parts by weight or more, and the anhydrosugar alcohol-alkylene oxide adduct and lipophilic polyol are contained in an amount of 84 parts by weight or less and 83 parts by weight or less, respectively. , may be included in an amount of 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

According to one embodiment, in the first method of producing the (meth)acrylic-modified polyurethane component, the reaction of the polyol component and polyisocyanate in step (1) is optionally performed using a catalyst (e.g., dibutyltin dilaurate). In the presence of a tin-based catalyst such as (DBTDL), at room temperature or at elevated temperature (e.g., 50 to 100° C., preferably 50 to 70° C.) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 hours to 0.5 hours). 2 hours), and the reaction between the reaction product of the polyol component and the polyisocyanate (i.e., the intermediate obtained from step (1)) and the hydroxyalkyl (meth)acrylate in step (2) is optionally carried out using a catalyst ( In the presence of a tin-based catalyst, such as dibutyltin dilaurate (DBTDL), at elevated temperature (e.g., 50 to 100° C., preferably 50 to 70° C.) for an appropriate time (e.g., 0.1 to 5 hours, preferably). It may be performed for 0.5 to 2 hours.

According to one embodiment, in the second manufacturing method of the (meth)acrylic-modified polyurethane component, based on a total of 100 parts by weight of the (meth)acrylic-modified polyurethane component to be produced, (i) hydrophilic (meth)acrylic 16 to 84 parts by weight of -modified polyurethane and 16 to 84 parts by weight of (ii) lipophilic (meth)acrylic-modified polyurethane may be mixed, more specifically, (i) hydrophilic and (ii) lipophilic (meth)acrylic ) Acrylic-modified polyurethane may be mixed in an amount of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, and the hydrophilic and lipophilic (meth)acrylic- Modified polyurethane may be mixed in an amount of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

The manufacturing methods for each of the (i) hydrophilic and (ii) lipophilic (meth)acrylic-modified polyurethanes mixed in the second manufacturing method of the (meth)acrylic-modified polyurethane component are as described above.

[(meth)acrylic-modified epoxy component]

The (meth)acrylic-modified epoxy component contained in the composition of the present invention is a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or these. It includes those selected from the group consisting of a combination of.

In one embodiment, the anhydrosugar alcohol-derived (meth)acrylic-modified epoxy compound may be represented by the following formula, but is not limited thereto:

Additionally, in one embodiment, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct may be represented by the following formula, but is not limited thereto:

In the above formula,

m and n each independently represent an integer from 0 to 15,

m+n is an integer from 1 to 30, more specifically an integer from 1 to 25, even more specifically an integer from 1 to 20, even more specifically an integer from 3 to 15, even more specifically an integer from 5 to 15 represents the integer of .

In one embodiment, the (meth)acrylic-modified epoxy component is a (meth)acrylic-modified epoxy resin derived from bisphenol, a (meth)acrylic-modified epoxy resin derived from phenol novolac, o-cresol It may further include a petroleum-based (meth)acrylic-modified epoxy resin selected from rockfish (Cresol novolac)-derived (meth)acrylic-modified epoxy resin, naphthol-derived (meth)acrylic-modified epoxy resin, or a combination thereof. there is.

<Anhydrosugar alcohol and anhydrosugar alcohol-alkylene oxide adduct>

The anhydrous sugar alcohol can be produced by dehydrating hydrogenated sugar derived from natural products. Hydrogenated sugar (also called “sugar alcohol”) refers to a compound obtained by adding hydrogen to the reducing terminal group of a saccharide, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer from 2 to 5) ) and is classified into tetritol, pentitol, hexitol, and heptitol (carbon numbers 4, 5, 6, and 7, respectively) depending on the carbon number. Among them, hexitol with 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

The anhydrosugar alcohol may be monoanhydrosugar alcohol, dianhydrosugar alcohol, or a mixture thereof. There is no particular limitation, but dianhydrosugar alcohol may be used.

Monohydrosugar alcohol 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 monosugar alcohol is not particularly limited, but is preferably monosususu hexitol, and more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol. , 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more of these.

Dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar. It has a diol form with two hydroxy groups in the molecule, and can be produced using hexitol derived from starch. Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest and research on its production method 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 is 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 anhydrosugar alcohol-alkylene oxide adduct (also referred to as “anhydrosugar alcohol-alkylene glycol”) has a hydroxy group at both ends or one end (preferably both ends) of the anhydrosugar alcohol. It is an adduct obtained by reacting alkylene oxide with a compound in which the hydrogen of the hydroxy group at both ends or one end (preferably both ends) of anhydrosugar alcohol is replaced with a hydroxyalkyl group, which is a ring-opened form of alkylene oxide. it means.

In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, it may be ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be a compound represented by the following formula (3) or a mixture of two or more thereof.

[Formula 3]

In Formula 3 above,

R ¹ and R ² each independently represent a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms,

m and n each independently represent an integer from 0 to 15,

m+n represents an integer from 1 to 30.

More preferably, in Formula 3,

R ¹ and R ² each independently represent an ethylene group, a propylene group, or an isopropylene group, and preferably R ¹ and R ² are the same as each other,

m and n each independently represent an integer from 0 to 14,

However, m+n is an integer of 1 or more, 2 or more, or 3 or more, and is also an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably 2 to 20. It represents an integer, more preferably an integer of 3 to 15.

In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct is an anhydrosugar alcohol-propylene oxide adduct represented by the following formula 3-1, an anhydrosugar alcohol-ethylene oxide adduct represented by the following formula 3-2, or It may be a mixture of these.

[Formula 3-1]

In Formula 3-1,

a and b each independently represent an integer from 0 to 15,

a+b represents an integer from 1 to 30.

More preferably, in Formula 3-1,

a and b each independently represent an integer from 0 to 14,

However, a+b is an integer of 1 or more, 2 or more, or 3 or more, and is also an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably 2 to 20. It represents an integer, more preferably an integer of 3 to 15.

[Formula 3-2]

In Formula 3-2,

c and d each independently represent an integer from 0 to 15,

c+d represents an integer from 1 to 30.

More preferably, in Formula 3-2,

c and d each independently represent an integer from 0 to 14,

However, c+d is an integer of 1 or more, 2 or more, or 3 or more, and is also an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably 2 to 20. It represents an integer, more preferably an integer of 3 to 15.

In one embodiment, the anhydrous sugar alcohol-alkylene oxide adduct comprises the steps of (1) treating anhydrous sugar alcohol with an acid component; And (2) it may be manufactured by a production method comprising the step of adding reaction between anhydrous sugar alcohol treated with the acid component obtained in step (1) and alkylene oxide.

More specifically, the anhydrous sugar alcohol-alkylene oxide adduct includes the steps of (1) treating anhydrous sugar alcohol with an acid component; (2) adding anhydrous sugar alcohol treated with the acid component obtained in step (1) and alkylene oxide; and (3) subjecting the product obtained in step (2) to an addition reaction with alkylene oxide in the presence of a base catalyst.

The acid component is not particularly limited, and may be selected from the group consisting of phosphoric acid, sulfuric acid, acetic acid, formic acid, heteropoly acid, or mixtures thereof. In one embodiment, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, or silicomolybdic acid may be used as the heteropoly acid, and others may be used. As an acid component, a commercially available acid component such as Amberlyst 15 (manufactured by Dow Chemical) may be used.

In one embodiment, the acid treatment uses 0.1 to 10 mol, preferably 0.1 to 8 mol, more preferably 0.1 to 5 mol of acid component per mole of anhydrosugar alcohol, and the temperature is raised under a nitrogen atmosphere. It may be performed at a temperature (e.g., 80°C to 200°C or 90°C to 180°C), and then vacuum decompression may be performed to remove moisture in the reactor, but is not limited thereto.

The acid component used in the acid treatment is to facilitate ring opening of alkylene oxide in the addition reaction of alkylene oxide, which will be described later.

Generally, the reaction of adding alkylene oxide to alcohol proceeds under a base catalyst. In the case of anhydrous sugar alcohol, due to its structural characteristics, the rate at which alkylene oxide is added and the ring structure of anhydrous sugar alcohol are ring-opened and decomposed by the base catalyst. There is competition in terms of speed. Accordingly, not only anhydrous sugar alcohol but also the decomposition product of anhydrous sugar alcohol reacts with alkylene oxide, and the reaction product between the decomposition product of anhydrous sugar alcohol decomposed by a base catalyst and alkylene oxide causes quality problems and lowers storage stability of the product. It can act as a factor. However, if anhydrous sugar alcohol is first treated with an acid component and then alkylene oxide is added to the reaction, the acid component not only facilitates ring opening of the alkylene oxide, but also does not produce decomposition products of anhydrous sugar alcohol by the base catalyst. , Anhydrosugar alcohol-alkylene oxide adduct can be easily produced by the addition reaction of anhydrosugar alcohol and alkylene oxide. Therefore, when an addition reaction is performed between acid-treated anhydrous sugar alcohol and alkylene oxide, conventional problems can be solved.

In one embodiment, the addition reaction of the anhydrous sugar alcohol treated with the acid component and the alkylene oxide is carried out at an elevated temperature (e.g., from 100° C. to 100° C.) while gradually adding the alkylene oxide to the anhydrous sugar alcohol treated with the acid component. The reaction may be performed at 180°C or 120°C to 160°C for, for example, 1 hour to 8 hours or 2 hours to 4 hours, but is not limited thereto. The molar ratio of the anhydrous sugar alcohol and alkylene oxide is, for example, It is 1 mol or more or 2 mol or more of alkylene oxide per mole of sugar alcohol, and is also 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, for example, 1 mol to 30 mol, preferably 2 to 20 mol. However, it is not limited to this.

In one embodiment, the addition reaction of the product obtained by the addition reaction of the alkylene oxide with additional alkylene oxide is performed, for example, in a high pressure reactor capable of pressurization (e.g., pressure of 3 MPa or more), using a base catalyst (e.g. For example, in the presence of a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide or a hydroxide of an alkaline earth metal such as calcium hydroxide), at an elevated temperature (e.g., 100°C to 180°C or 120°C to 160°C, for example, for 1 hour) It may be carried out for 8 hours or 2 to 4 hours, but the reaction molar ratio of anhydrous sugar alcohol and alkylene oxide is, for example, 1 mole or more, 2 mole or more per mole of anhydrous sugar alcohol. It may be 3 mol or more, and also 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, for example, 1 mol to 30 mol, preferably 2 to 20 mol, more preferably 3 to 15 mol. , but is not limited to this. Before adding the base catalyst, the acid component used in the treatment may be removed by filtration.

The product obtained from the addition reaction of acid-treated anhydrous sugar alcohol and alkylene oxide (i.e., a compound in which alkylene oxide is added to anhydrous sugar alcohol) has a very stable structure, so even in the presence of a base catalyst, it can be easily converted to anhydrous sugar at high temperatures. The ring structure of alcohol is not ring-opened or decomposed. Therefore, it is very advantageous to additionally carry out an addition reaction with alkylene oxide. If the acid catalyst is continued to be used during the additional addition reaction of alkylene oxide, the acid catalyst helps promote ring opening of alkylene oxide, but the reaction rate decreases as the added mole number of alkylene oxide increases. In other words, the rate at which alkylene oxide is added competes with the rate at which the alkylene oxide itself is ring-opened. At this time, the rate at which alkylene oxide is added slows down, and self-condensation reaction and by-product generation between the ring-opened alkylene oxides proceed. This may cause quality deterioration. Therefore, the additional addition reaction of alkylene oxide proceeds under a base catalyst.

Thereafter, a step of removing metal ions flowing out from the used base catalyst can be additionally performed. For this purpose, a metal ion adsorbent such as Ambosol MP20 (magnesium silicate component) can be used.

<Polyisocyanate>

In one embodiment, the polyisocyanate is, for example, methylenediphenyl diisocyanate (MDI) (e.g., 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, etc. aromatic polyisocyanate; 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) (e.g. 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (e.g. cyclohexane-1,4-diisocyanate) or ethylene diisocyanate. aliphatic polyisocyanates such as; Or it may be a combination thereof, but is not limited thereto.

In another embodiment, the polyisocyanate is methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexa Hydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6 -Toluene diisocyanate, toluene diisocyanate mixed with 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4-/2,6-isomer ratio = 80/20), diphenylmethane-2, It may be 4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or a combination 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.

<Hydroxyalkyl (meth)acrylate>

In one embodiment, the hydroxyalkyl (meth)acrylate may be, for example, a linear or branched alkyl acrylate having a hydroxy group, a linear or branched alkyl methacrylate having a hydroxy group, or a combination thereof. Specifically, hydroxy-C _1-8 alkyl (meth)acrylate, that is, linear C _1-8 alkyl acrylate having a hydroxy group, branched C _3-8 alkyl acrylate having a hydroxy group, linear C ₁ having a hydroxy group. _-8 alkyl methacrylate, branched C _3-8 alkyl methacrylate having a hydroxy group, or a combination thereof, and more specifically, hydroxymethyl acrylate, hydroxymethyl methacrylate, and hydroxyethyl acrylate. , hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, hydroxypentyl methacrylate, 2-hydroxide Roxyethylhexyl acrylate, 2-hydroxyethylhexyl methacrylate, 2-hydroxyethylbutyl acrylate, 2-hydroxyethylbutyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate or these It may be a combination, but is not limited thereto.

More specifically, the hydroxyalkyl (meth)acrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, It may be hydroxybutyl methacrylate or a combination thereof.

[(meth)acrylic monomer]

The (meth)acrylic monomer included in the anaerobic adhesive composition of the present invention improves workability such as application on an adhesive substrate by controlling the viscosity of the anaerobic adhesive composition, improves the anaerobic curing speed of the anaerobic adhesive composition, and improves the cured product. Adhesion can be improved by improving the strength.

In one embodiment, the (meth)acrylic monomer included in the composition of the present invention may be one or more monomers having 1 to 4 (meth)acrylic groups in the molecule.

Examples of the (meth)acrylic monomer having one (meth)acrylic group in the molecule include (meth)acrylic acid, lauryl (meth)acrylate, stearyl (meth)acrylate, and ethylcarbitol ( Meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclofentanyl (meth)acrylate, isobornyl (meth) ) Acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, nonylphenok Cyethyl (meth)acrylate, nonylphenoxytetraethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethyl (meth)acrylate, Toxytriethylene glycol (meth)acrylate, 2-ethylhexylpolyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycidyl (meth)acrylate Latex, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichloro. Hydrin (hereinafter abbreviated as ECH)-modified butyl (meth)acrylate, ECH-modified phenoxy (meth)acrylate, ethylene oxide (hereinafter abbreviated as EO)-modified phthalic acid (meth)acrylate, EO-modified Succinic acid (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, ( Examples include, but are not limited to, 2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, or combinations thereof.

In addition, examples of the (meth)acrylic monomer having two or more (e.g., 2 to 4) (meth)acrylic groups in the molecule include 1,6-hexanediol diacrylate (1,6). -hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), tripropylene glycol diacrylate (TPGDA), bisphenol A [EO]4~30 diacrylate (bisphenol A [EO]4) ~30 diacrylate, BPA[EO]4~30DA, EO is ethylene oxide unit), trimethylolpropane triacrylate (TMPTA), trimethylolpropane [EO]3~15 triacrylate (trimethylolpropane [EO]3) ~15 triacrylate, TMP[EO]3~15TA, EO is ethylene oxide unit), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), ditrimethylolpropane tetraacrylate Examples include, but are not limited to, ditrimethylolpropane tetraacrylate (DTMPTTA), dipentaerylthritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), or a combination thereof.

[Peroxide radical initiator]

The anaerobic curing component included in the composition of the present invention is used to induce and promote curing under anaerobic conditions.

In one embodiment, the anaerobic curing component may include an anaerobic initiator and a curing accelerator.

In one embodiment, the anaerobic initiator may include a peroxide radical initiator.

In one embodiment, the peroxide radical initiator is a group consisting of cumene hydroperoxide, t-butyl hydroperoxide, methyl ethyl ketone hydroperoxide, para-menthane hydroperoxide, diisopropyl benzene hydroperoxide, or a combination thereof. It may include, but is not limited to, an organic hydroperoxide selected from the following.

In one embodiment, the anaerobic initiator may be included in a total of 100 parts by weight of the composition of the present invention, for example, in an amount of 0.1 to 10 parts by weight, more specifically, 0.1 part by weight or more, 0.2 parts by weight or more. , in an amount of 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more, and also in an amount of 10 parts by weight or less, 9.5 parts by weight or less, 9 parts by weight or less, 8.5 parts by weight or less, 8 parts by weight or less, or 7.5 parts by weight or less. may be included, but is not limited thereto.

In one embodiment, the curing accelerator may include one or more selected from the group consisting of saccharin, amine compound, organic hydrazine, maleic acid, quinone, or a combination thereof, but is not limited thereto.

In one embodiment, the amine compound consists of toluidine, N,N,-dimethyl-p-toluidine, N,N,-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, or a combination thereof. It may include one or more aromatic amines selected from the group, but is not limited thereto.

In one embodiment, in a total of 100 parts by weight of the composition of the present invention, the curing accelerator may be included in an amount of, for example, 0.5 parts by weight to 10 parts by weight, and more specifically, 0.5 parts by weight or more, 0.7 parts by weight or more. , in an amount of 1 part by weight or more, 1.2 parts by weight or more, or 1.5 parts by weight or more, and also in an amount of 10 parts by weight or less, 9.5 parts by weight or less, 9 parts by weight or less, 8.5 parts by weight or less, 8 parts by weight or less, or 7.5 parts by weight or less. may be included, but is not limited thereto.

[Optional additional additives]

In addition to the ingredients described above, the compositions of the present invention may optionally include one or more additional additives.

In one embodiment, the additional additive may include, but is not limited to, one or more selected from the group consisting of a polymerization inhibitor, a chelating agent, or a combination thereof.

The optionally used polymerization inhibitor may be used to improve the storage stability of the composition before use by inhibiting the room temperature curing reaction in the composition that occurs naturally when the composition is stored when not in use.

In one embodiment, the polymerization inhibitor is hydroquinone (HQ), 4-methoxyphenol, methylhydroquinone, hydroquinone monomethyl ether (MEHQ), hydroquinone monoethyl ether (EEHQ), naphthoquinone, anthraquinone, or It may be selected from the group consisting of a combination of these, but is not limited thereto.

Chelating agents, optionally used, can be used to capture trace metal impurities in the composition.

In one embodiment, the chelating agent may be the tetra-sodium salt of ethylenediamine tetra acetic acid (EDTA), but is not limited thereto.

In one embodiment, in a total of 100 parts by weight of the composition of the present invention, each of the above additional additives may be included in an amount of, for example, 0.0001 to 2 parts by weight, more specifically, 0.001 or more parts by weight, 0.005 parts by weight. It may be included in an amount of more than 0.01 part by weight, more than 0.05 part by weight, or more than 0.1 part by weight, and also in an amount of less than 2 parts by weight, less than 1.5 part by weight, less than 1 part by weight, less than 0.8 part by weight, or less than 0.5 part by weight. However, it is not limited to this.

If the content of each additional additive is excessively lower than the above level, the effect of using the additive may be insignificant, and if it is excessively higher than the above level, the curing speed may be delayed under anaerobic conditions.

[Method for producing anaerobic adhesive composition and article to which the composition is applied]

According to another aspect of the present invention, a (meth)acrylic-modified polyurethane component comprising a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; A (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Epoxy component; (meth)acrylic monomer; and an anaerobic curing component; wherein the content of the (meth)acrylic-modified polyurethane component is greater than 18 parts by weight and less than 65 parts by weight in a total of 100 parts by weight of the mixture; The content of the (meth)acrylic-modified epoxy component is greater than 12 parts by weight and less than 45 parts by weight; The (meth)acrylic monomer content is greater than 7 parts by weight and less than 50 parts by weight; Consists of the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. A method for producing an anaerobic adhesive composition is provided, characterized in that the total content of those selected from the group is greater than 10 parts by weight and less than 70 parts by weight.

In the method for producing the anaerobic adhesive composition, a (meth)acrylic-modified polyurethane component; (meth)acrylic-modified epoxy component; (meth)acrylic monomer; and anaerobic curing components are as described above.

In one embodiment, a mixture of the components described above (i.e., (meth)acrylic-modified polyurethane component; (meth)acrylic-modified epoxy component; (meth)acrylic monomer; and anaerobic curing component, and optional additional additives) Can be performed in an environment controlled at 60°C or lower (e.g., 10 to 60°C).

According to another aspect of the present invention, an article to which the anaerobic adhesive composition of the present invention is applied is provided.

In one embodiment, the article is made of metal; and a coating layer coated on the surface of the metal material, wherein the coating layer may include the anaerobic adhesive composition of the present invention.

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 to these.

[Example]

<Preparation of anhydrosugar alcohol-alkylene oxide adduct>

Preparation Example 1: Preparation of isosorbide-ethylene oxide 5 mol adduct

146 g of isosorbide was placed in a pressurized reactor, 0.15 g of phosphoric acid (85%) was added as an acid component, the inside of the reactor was replaced with nitrogen and heated to 100°C, and the inside of the reactor was reduced by vacuum. Moisture was removed. Then, 88 g of ethylene oxide was gradually added into the reactor and reacted at a temperature of 100°C to 140°C for 2 to 3 hours. At this time, the reaction temperature was adjusted so that the reaction temperature did not exceed 140°C. Afterwards, the internal temperature of the reactor was cooled to 50°C, 0.3 g of potassium hydroxide was added to the reactor, the inside of the reactor was replaced with nitrogen, heated to 100°C, and moisture in the reactor was removed through vacuum decompression. Then, 132 g of ethylene oxide was slowly added a second time, and reaction was performed at 100°C to 140°C for 2 to 3 hours. When the reaction was completed, the internal temperature of the reactor was cooled to 50°C, 4.0 g of Ambosol MP20 as an adsorbent was added, and the mixture was heated again and stirred at a temperature of 100°C to 120°C for 1 to 5 hours to remove metal ions. At this time, the inside of the reactor was replaced with nitrogen and/or vacuum decompression was performed. When metal ions were no longer detected, the internal temperature of the reactor was cooled to 60°C to 90°C, and then residual by-products were removed to obtain 362 g of a 5 molar isosorbide-ethylene oxide adduct in the form of a transparent liquid.

Preparation Example 2: Preparation of 10 mole isosorbide-ethylene oxide adduct

Except that the secondary amount of ethylene oxide added was changed from 132 g to 352 g, the same method as in Preparation Example 1 was performed to obtain 551 g of a transparent liquid isosorbide-ethylene oxide 10 mole adduct.

Preparation Example 3: Preparation of isosorbide-propylene oxide 5 mol adduct

Instead of using ethylene oxide as the addition reaction raw material, propylene oxide was used. Specifically, instead of adding 88g of ethylene oxide first, 116g of propylene oxide was added first, and instead of adding 132g of ethylene oxide secondarily, 174g of propylene oxide was added as a second addition. Except for adding tea, the same method as Preparation Example 1 was performed to obtain 423 g of a transparent liquid isosorbide-propylene oxide 5 mole adduct.

Preparation Example 4: Preparation of 10 mole isosorbide-propylene oxide adduct

Instead of using ethylene oxide as the addition reaction raw material, propylene oxide was used. Specifically, instead of adding 88g of ethylene oxide first, 116g of propylene oxide was added first, and instead of adding 132g of ethylene oxide secondarily, 465g of propylene oxide was added as a second addition. Except for adding tea, the same method as Preparation Example 1 was performed to obtain 698 g of a 10 mole isosorbide-propylene oxide adduct in the form of a transparent liquid.

<Manufacture of (meth)acrylic-modified polyurethane component>

Preparation Example A1: Using 5 mole isosorbide-ethylene oxide adduct as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate (meth) )Manufacture of acrylic modified polyurethane

222 g of isophorone diisocyanate (IPDI) and 0.1 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst were added to a three-neck glass reactor equipped with a stirrer and mixed at room temperature, and the isosorbide-ethylene obtained in Preparation Example 1 was added. A crosslinking reaction was performed by slowly adding 183 g of 5 mole oxide adduct. After completing the addition of 5 mol of isosorbide-ethylene oxide adduct, the mixture was aged and stirred at 50°C for 1 hour, and then 65 g of 2-hydroxyethyl methacrylate was slowly added to perform an acrylic modification reaction. After completing the addition of 2-hydroxyethyl methacrylate, the mixture was aged and stirred at 50°C for 1 hour, and then the reaction product was cooled to room temperature to obtain 467 g of (meth)acrylic-modified polyurethane of the following formula (A).

[Formula A]

Preparation Example A2: Using 10 mole isosorbide-ethylene oxide adduct as polyol, hexamethylene diisocyanate (HDI) as polyisocyanate, and 2-hydroxyethyl acrylate as hydroxyalkyl (meth)acrylate (meth) Acrylic modified polyurethane manufacturing

As a polyisocyanate, 168 g of hexamethylene diisocyanate (HDI) was used instead of isophorone diisocyanate (IPDI), and as a polyol, 5 mol of isosorbide-ethylene oxide obtained in Preparation Example 1 was used in Preparation Example 2. 293 g of the obtained 10 mole isosorbide-ethylene oxide adduct was used, except that 58 g of 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate as the hydroxyalkyl (meth)acrylate. By performing the same method as Preparation Example A1, 515 g of (meth)acrylic modified polyurethane of the following formula B was obtained.

[Formula B]

Preparation Example A3: Using 5 mole isosorbide-propylene oxide adduct as polyol, methylenediphenyl diisocyanate (MDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate ( Met) Acrylic modified polyurethane manufacturing

As the polyisocyanate, 250 g of methylenediphenyl diisocyanate (MDI) was used instead of isophorone diisocyanate (IPDI), and as the polyol, 5 mol of the isosorbide-ethylene oxide adduct obtained in Preparation Example 1 was used in Preparation Example 3. By carrying out the same method as Preparation Example A1, except that 218 g of 5 mole isosorbide-propylene oxide adduct obtained in was used, 529 g of (meth)acrylic modified polyurethane of the following formula C was obtained.

[Formula C]

Preparation Example A4: Using 10 mole isosorbide-propylene oxide adduct as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate (meth) )Manufacture of acrylic modified polyurethane

The same method as Preparation Example A1 except that 363 g of the 10 mole isosorbide-propylene oxide adduct obtained in Preparation Example 4 was used as the polyol instead of the 5 mole isosorbide-ethylene oxide adduct obtained in Preparation Example 1. By performing, 643 g of (meth)acrylic modified polyurethane of the following formula D was obtained.

[Formula D]

Preparation Example A5: Polypropylene glycol (80 parts by weight based on 100 parts by weight of total polyol) and 5 mole isosorbide-ethylene oxide adduct (20 parts by weight based on 100 parts by weight of total polyol) as polyol, isophorone diisocyanate as polyisocyanate (IPDI), preparation of (meth)acrylic-modified polyurethane component using 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate

600 g of isophorone diisocyanate (IPDI) and 0.6 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst were added to a three-neck glass reactor equipped with a stirrer and mixed at room temperature, while polypropylene glycol (number average molecular weight: 1,000) was added as a polyol. A crosslinking reaction was performed by slowly adding 800 g of g/mol (manufactured by Kumho Petrochemical Co., Ltd.) and 200 g of the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1. After completing the addition of the polyol component, the mixture was aged and stirred at 50°C for 1 hour, and then 350 g of 2-hydroxyethyl methacrylate was slowly added to perform an acrylic modification reaction. After completing the addition of 2-hydroxyethyl methacrylate, the reaction product was aged and stirred at 50°C for 1 hour, and the reaction product was cooled to room temperature to produce 390 g of (meth)acrylic-modified polyurethane of the formula A below and (meth) of the formula E below. 1,950 g of (meth)acrylic-modified polyurethane component containing 1,560 g of acrylic-modified polyurethane was obtained.

[Formula A]

[Formula E]

Preparation Example A6: Polytetrahydrofuran (50 parts by weight based on 100 parts by weight of total polyol) and 10 mole isosorbide-ethylene oxide adduct (50 parts by weight based on 100 parts by weight of total polyol) as polyol, hexamethylene di as polyisocyanate Production of (meth)acrylic-modified polyurethane components using 2-hydroxyethyl acrylate as isocyanate (HDI) and hydroxyalkyl (meth)acrylate

As polyisocyanate, 270 g of hexamethylene diisocyanate (HDI) was used instead of isophorone diisocyanate (IPDI), and as polyol, polypropylene glycol (number average molecular weight: 1,000 g/mol, manufactured by Kumho Petrochemical Co., Ltd.) and preparation example Instead of 5 mol of isosorbide-ethylene oxide adduct obtained in 1, 365 g of polytetrahydrofuran (number average molecular weight: 2,000 g/mol, Aldrich Co., Ltd.) and isosorbide-ethylene obtained in Preparation Example 2 Same as Preparation Example A5, except that 365 g of 10 mole oxide adduct was used, and 186 g of 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate. By carrying out the method, 1,185 g of a (meth)acrylic-modified polyurethane component containing 593 g of (meth)acrylic-modified polyurethane of the formula B below and 592 g of the (meth)acrylic-modified polyurethane of the formula F below was obtained.

[Formula B]

[Formula F]

Preparation Example A7: Polydimethylsiloxane diol (20 parts by weight based on 100 parts by weight of total polyol) and 5 mole isosorbide-propylene oxide adduct (80 parts by weight based on 100 parts by weight of total polyol) as polyol, methylenediphenyl as polyisocyanate Diisocyanate (MDI), manufacturing (meth)acrylic-modified polyurethane component using 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate

As polyisocyanate, 700 g of methylenediphenyl diisocyanate (MDI) was used instead of isophorone diisocyanate (IPDI), and as polyol, polypropylene glycol (number average molecular weight: 1,000 g/mol, manufactured by Kumho Petrochemical Co., Ltd.) Instead of 5 mol of isosorbide-ethylene oxide adduct obtained in Example 1, 140 g of polydimethylsiloxane diol (number average molecular weight: 1,000 g/mol, manufactured by Aldrich) and isosorbide obtained in Preparation Example 3- By carrying out the same method as Preparation Example A5 except that 560 g of 5 mol of propylene oxide adduct was used and the content of 2-hydroxyethyl methacrylate was changed from 350 g to 364 g, (meth)acrylic of the formula C below was prepared. - 1,763 g of (meth)acrylic-modified polyurethane component containing 1,410 g of modified polyurethane and 353 g of (meth)acrylic-modified polyurethane of the formula G below was obtained.

[Formula C]

[Formula G]

Preparation Example A8: Polytetrahydrofuran (30 parts by weight based on 100 parts by weight of total polyol) and 10 mole isosorbide-propylene oxide adduct (70 parts by weight based on 100 parts by weight of total polyol) as polyol, isophorone di as polyisocyanate Production of (meth)acrylic-modified polyurethane components using 2-hydroxyethyl methacrylate as isocyanate (IPDI) and hydroxyalkyl (meth)acrylate

As a polyol, polytetrahydrofuran (number average molecular weight) was used instead of polypropylene glycol (number average molecular weight: 1,000 g/mol, Kumho Petrochemical Co., Ltd.) and the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1. : 1,000 g/mol, Aldrich (manufactured by)) 324g and 746g of the 10 mol isosorbide-propylene oxide adduct obtained in Preparation Example 4 were used, by carrying out the same method as Preparation A5, to obtain the following chemical formula: 2,020 g of (meth)acrylic-modified polyurethane component containing 1,414 g of (meth)acrylic-modified polyurethane of D and 606 g of (meth)acrylic-modified polyurethane of the formula H below was obtained.

[Formula D]

[Formula H]

Preparation Example A9: (meth)acrylic modification using polydimethylsiloxane (PDMS) polyol as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate. polyurethane manufacturing

As a polyol, 1,000 g of polydimethylsiloxane (PDMS) polyol (number average molecular weight: 1,000 g/mol, manufactured by Momentive Co., Ltd.) was used instead of 5 mol of isosorbide-ethylene oxide adduct obtained in Preparation Example 1. By carrying out the same method as Preparation Example A1 except, 1,280 g of (meth)acrylic modified polyurethane of the following formula (I) was obtained.

[Formula I]

Preparation Example A10: Preparation of (meth)acrylic-modified polyurethane using polypropylene glycol as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate.

Except that 1,349 g of polypropylene glycol (number average molecular weight: 1,000 g/mol, manufactured by Kumho Petrochemical Co., Ltd.) was used as the polyol instead of the 5 mole isosorbide-ethylene oxide adduct obtained in Preparation Example 1. By carrying out the same method as Preparation Example A1, 1,630 g of (meth)acrylic-modified polyurethane of the following formula (J) was obtained.

[Formula J]

Preparation Example A11: (meth)acrylic modified polyurethane using polytetramethylene glycol as polyol, methylenediphenyl diisocyanate (MDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate. manufacturing

As polyisocyanate, 250 g of methylenediphenyl diisocyanate (MDI) was used instead of isophorone diisocyanate (IPDI), and as polyol, polytetramethylene was used instead of 5 mole isosorbide-ethylene oxide adduct obtained in Preparation Example 1. By carrying out the same method as Preparation Example A1, except that 1,000 g of glycol (number average molecular weight: 1,000 g/mol, Aldrich Co., Ltd.) was used, 1,308 g of (meth)acrylic modified polyurethane of the formula K below was prepared. Obtained.

[Formula K]

<Preparation of (meth)acrylic-modified epoxy compounds derived from anhydrosugar alcohol and anhydrosugar alcohol-alkylene oxide adduct>

Preparation Example B1: Preparation of (meth)acrylic-modified epoxy compound derived from anhydrous sugar alcohol

In a three-neck glass reactor equipped with a stirrer, 100 g of isosorbide diglycidyl ether of the formula L (manufactured by Cheil Chemical) as reaction raw materials, 500 g of methacrylic acid, 2 mL of triethylamine as a catalyst, and Mequinol as a polymerization inhibitor. After adding 0.5 g (manufactured by Aldrich Co., Ltd.), the acrylic modification reaction was performed by stirring for 5 hours at 100°C in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove unreacted methacrylic acid. The residue from which unreacted methacrylic acid was removed was diluted with 1.0 L of ethyl acetate, washed sequentially with 1 L of 20% aqueous sodium bicarbonate solution and 1 L of distilled water, and distilled under reduced pressure to obtain (meth) derived from isosorbide of the formula M below. 125 g of acrylic-modified epoxy compound (DGEI-AA) was obtained.

[Formula L]

[Formula M]

Preparation Example B2: Preparation of (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct

After filling a three-neck glass reactor equipped with a stirrer with 900 mL of chloroform, 183 g of the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1 as reaction raw materials, 142 g of glycidyl methacrylate, and triethyl as a catalyst. After adding 3 mL of amine, the reaction proceeded by heating and stirring the reaction mixture at 70°C in a nitrogen atmosphere for 48 hours. After completion of the reaction, the reaction mixture was sequentially washed with 500 mL of 1N HCl aqueous solution and distilled water, and distilled under reduced pressure to obtain a (meth)acrylic-modified epoxy compound derived from a 5 mole isosorbide-ethylene oxide adduct of the formula N (DGEI- 210 g of E5-AA) was obtained.

[Formula N]

<Preparation of anaerobic adhesive composition>

Examples A1 to A10 and Comparative Examples A1 to A9: Standard Preparation Method

A liquid anaerobic adhesive composition was prepared by adding the components of the types and amounts (indicated in parentheses) listed in Table 1 below into a mixing reactor managed at 60°C or lower and mixing them with stirring at a temperature of 60°C or lower.

[Description of ingredients used]

2-HEMA: 2-Hydroxyethyl metharylate (manufactured by Samjeon Pure Pharmaceutical)

4-HBA: 4-Hydroxybutyl acrylate (manufactured by Samjeon Pure Pharmaceutical)

BA: Butyl acrylate (manufactured by Samjeon Pure Pharmaceutical)

PETTA: Pentaerythritol Tetraacrylate (manufactured by Miwon Corporation)

P-2M: 2-Methacryloyloxyethyl acid phoshate (manufactured by Kyoeisha Co., Ltd. (Japan))

BDDA: 1,4-Butanediol Diacrylate (manufactured by Aldrich)

KDU1100: Bisphenol A epoxy diacrylate (manufactured by Kukdo Chemical)

CHP: Cumene hydroperoxide (manufactured by Aldrich)

BHP: t-butyl hydroperoxide (manufactured by Aldrich)

Sac: Saccharin

DEpT: N,N-Diethyl-p-toluidine (manufactured by Aldrich)

DMoT: N,N-Dimethyl-o-toluidine (manufactured by Aldrich)

MEHQ: 4-Methoxyphenol (manufactured by Aldrich)

EDTA: Ethylene-diamine-tetraacetic acid (manufactured by Daejeong Chemical)

<Evaluation of physical properties of anaerobic adhesive composition>

(1) Room temperature adhesion and oil resistance evaluation

The anaerobic adhesive composition prepared in Examples A1 to A10 and Comparative A1 to A9 was applied to the surfaces of two rolled steel plates (manufactured by POSCO) cut to a size of 2.5 cm wide x 12 cm long, with an area of 2.5 cm wide x 2.0 cm long. were applied to each, and an assembly was manufactured by overlapping and clamping the applied areas. At this time, in the assembly, the joint between the two rolled steel plates to which the anaerobic adhesive composition was applied was in an anaerobic state in which air was completely blocked. Afterwards, the assembly was cured at room temperature (25 ± 5°C) for 5 days to prepare a metal adhesive specimen. For each of the above specimens, room temperature adhesion and oil resistance were evaluated by the following methods, and the results are shown in Table 2 below.

[Room temperature adhesiveness]

In order to evaluate the metal adhesion of the anaerobic adhesive composition to the rolled steel plate, the shear strength (Lap shear strength) of each metal adhesive specimen prepared above using UTM (Instron 5967 product, manufactured by Instron) (unit: MPa) was measured. Specifically, the shear strength was measured a total of five times for each metal bonded specimen, and then the average value was calculated. A higher shear strength means better metal adhesion.

[Oil resistance]

The prepared metal adhesive specimens were immersed in mineral oil (Daejeong Chemical Co., Ltd.) and heated at 190°C for 200 hours, and then the shear strength of each immersed metal adhesive specimen was measured five times using the room temperature adhesive measurement method described above. Measurements were made, and the average value was calculated. Afterwards, the shear strength reduction rate (%) after immersion compared to the shear strength before immersion of each metal bonded specimen was calculated. At this time, the lower the shear strength reduction rate, the better the oil resistance.

Shear strength reduction rate (%) =

(Shear strength before immersion - Shear strength after immersion) / (Shear strength before immersion) x 100

(2) Room temperature impact strength (unit: N/mm) evaluation

The room temperature impact strength was measured as follows based on ISO 11343 standards.

A steel specimen measuring 90 mm in length

After applying each of the anaerobic adhesive compositions obtained in Examples A1 to A10 and Comparative Examples A1 to A9 on the adhesive surface at the end of 30 mm, a small amount of microbeads were layered thereon to maintain a constant adhesive thickness. Afterwards, another steel specimen was covered and fixed on top and cured at room temperature (25±5°C) for 5 days. After curing, the room temperature impact strength of the adhesive specimen cooled to room temperature was measured using a drop impact tester. At this time, the room temperature impact strength was measured by passing the wedge jig through the adhesive portion of the adhesive portion, and the impact speed was conducted at 2 m/s to 3 m/s. At this time, the room temperature impact strength of each specimen was measured five times and the average value was calculated, and the results are shown in Table 2 below.

As shown in Table 2, in the case of the anaerobic adhesive compositions of Examples A1 to A10 according to the present invention, the shear strength was 16 MPa or more, showing excellent room temperature adhesiveness, and the room temperature impact strength was also maintained at 27 N/mm or more. The room temperature impact resistance was excellent, and the shear strength reduction rate was maintained below 21% even after the adhesive specimen was immersed in mineral oil for 200 hours at 190°C, showing that the oil resistance was also excellent.

However, in terms of the total content of the hydrophilic (meth)acrylic-modified polyurethane and the (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol and/or anhydrosugar alcohol-alkylene oxide adduct, in the case of Comparative Example A1, oil resistance This was poor and the room temperature impact resistance was poor. In the case of Comparative Example A2, the room temperature adhesiveness and room temperature impact resistance were poor. Additionally, in the case of Comparative Example A3, which did not contain hydrophilic (meth)acrylic-modified polyurethane, oil resistance was very poor. In addition, in terms of the content of the (meth)acrylic-modified polyurethane component, in the case of Comparative Example A4, the oil resistance was reduced and the impact resistance at room temperature was very poor, and in the case of Comparative Example A5, the adhesiveness at room temperature was very poor and the room temperature adhesion was very poor. Impact resistance decreased. In addition, in terms of (meth)acrylic monomer content, in the case of Comparative Example A6, room temperature adhesiveness was very poor, and in the case of Comparative Example A7, oil resistance and room temperature impact resistance were very poor. In addition, in terms of the content of the (meth)acrylic-modified epoxy component, in the case of Comparative Example A8, room temperature adhesiveness and oil resistance were very poor, and in the case of Comparative Example A9, the room temperature impact resistance was very poor.

As described above, in the case of the anaerobic adhesive composition according to the present invention, it was confirmed that not only was the room temperature adhesion to metal and room temperature impact resistance excellent, but the adhesive strength was maintained even in high temperature oil, and oil resistance was also excellent at the same time.

Claims (15)

(meth)acrylic-modified polyurethane components including hydrophilic (meth)acrylic-modified polyurethane and lipophilic (meth)acrylic-modified polyurethane;
A (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Epoxy component;
(meth)acrylic monomer; and
Contains an anaerobic curing component;
Based on a total of 100 parts by weight of the composition,
The (meth)acrylic-modified polyurethane component content is greater than 18 parts by weight and less than 65 parts by weight;
The content of the (meth)acrylic-modified epoxy component is greater than 12 parts by weight and less than 45 parts by weight;
The (meth)acrylic monomer content is greater than 7 parts by weight and less than 50 parts by weight;
Consists of the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. The total content of those selected from the group is more than 10 parts by weight and less than 70 parts by weight,
Anaerobic adhesive composition. According to paragraph 1,
Hydrophilic (meth)acrylic-modified polyurethanes include polymerized units derived from anhydrosugar alcohol-alkylene oxide adducts; polymerized units derived from polyisocyanates; and polymerized units derived from hydroxyalkyl (meth)acrylates,
Lipophilic (meth)acrylic-modified polyurethanes include polymerized units derived from lipophilic polyols; polymerized units derived from polyisocyanates; and polymerized units derived from hydroxyalkyl (meth)acrylate,
Anaerobic adhesive composition. The method of claim 2, wherein the anhydrosugar alcohol-alkylene oxide adduct is obtained by reacting a hydroxyl group at both ends or one end of anhydrosugar alcohol with alkylene oxide, wherein the alkylene oxide is a linear or linear form having 2 to 8 carbon atoms. An anaerobic adhesive composition, which is a branched alkylene oxide having 3 to 8 carbon atoms. 4. The anaerobic adhesive composition of claim 3, wherein the anhydrosugar alcohol is dianhydrosugar hexitol. 3. The anaerobic adhesive composition of claim 2, wherein the lipophilic polyol is selected from polytetramethylene glycol, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or combinations thereof. The method of claim 1, wherein the (meth)acrylic-modified epoxy component is a (meth)acrylic-modified epoxy resin derived from bisphenol, a (meth)acrylic-modified epoxy resin derived from phenol novolak, or (meth)acrylic-modified epoxy resin derived from o-cresol novolak. ) An anaerobic adhesive composition further comprising a petroleum-based (meth)acrylic-modified epoxy resin selected from an acrylic-modified epoxy resin, a naphthol-derived (meth)acrylic-modified epoxy resin, or a combination thereof. The anaerobic adhesive composition according to claim 1, wherein the (meth)acrylic monomer is a monomer having 1 to 4 (meth)acrylic groups in the molecule. The anaerobic adhesive composition of claim 1, wherein the anaerobic curing component includes an anaerobic initiator and a curing accelerator. The method of claim 8, wherein the anaerobic initiator is selected from the group consisting of cumene hydroperoxide, t-butyl hydroperoxide, methylethyl ketone hydroperoxide, para-menthane hydroperoxide, diisopropyl benzene hydroperoxide, or combinations thereof. An anaerobic adhesive composition comprising a selected organic hydroperoxide. The anaerobic adhesive composition of claim 8, wherein the curing accelerator includes one or more selected from the group consisting of saccharin, amine compounds, organic hydrazine, maleic acid, quinone, or combinations thereof. The method of claim 10, wherein the amine compound consists of toluidine, N,N,-dimethyl-p-toluidine, N,N,-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, or a combination thereof. An anaerobic adhesive composition comprising at least one aromatic amine selected from the group. The anaerobic adhesive composition of claim 1, further comprising an additive selected from the group consisting of a polymerization inhibitor, a chelating agent, or a combination thereof. (meth)acrylic-modified polyurethane components including hydrophilic (meth)acrylic-modified polyurethane and lipophilic (meth)acrylic-modified polyurethane; A (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol, a (meth)acrylic-modified epoxy compound derived from anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Epoxy component; (meth)acrylic monomer; And mixing an anaerobic curing component,
As a result, in a total of 100 parts by weight of the mixture, the content of the (meth)acrylic-modified polyurethane component is more than 18 parts by weight and less than 65 parts by weight; The content of the (meth)acrylic-modified epoxy component is greater than 12 parts by weight and less than 45 parts by weight; The (meth)acrylic monomer content is greater than 7 parts by weight and less than 50 parts by weight; Consists of the hydrophilic (meth)acrylic-modified polyurethane, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol, the (meth)acrylic-modified epoxy compound derived from the anhydrosugar alcohol-alkylene oxide adduct, or a combination thereof. Characterized in that the total content of those selected from the group is greater than 10 parts by weight and less than 70 parts by weight,
Method for producing an anaerobic adhesive composition. An article to which the anaerobic adhesive composition of any one of claims 1 to 12 is applied. The method of claim 14, comprising: a metal material; and a coating layer coated on the surface of the metal material, wherein the coating layer includes the anaerobic adhesive composition of any one of claims 1 to 12.