KR102274506B1 - Room temperature curing type acrylic adhesive composition - Google Patents

Abstract

The present invention relates to a room temperature-cured acrylic adhesive composition, and more specifically, to a room temperature-cured acrylic adhesive composition, which is provided to solve the above problems and can realize excellent adhesion while preventing loss of energy, manpower, production time and the like and damage to an adherend due to conventional heat treatment by providing an acrylic adhesive that is cured at room temperature without a separate heat treatment process and expresses adhesion.

Description

Room temperature curing type acrylic adhesive composition {ROOM TEMPERATURE CURING TYPE ACRYLIC ADHESIVE COMPOSITION}

The present invention relates to an acrylic adhesive composition that is cured at room temperature without a separate heat treatment process to express adhesive strength.

In general, sheets used for walls in various fields (such as various buildings or ships) are usually fiber reinforced sheets (glass fabric) and PVC (polyvinyl chloride) sheets in order to block noise and vibration and to provide insulation functions. adhesive) and EVA (ethylene vinyl acetate) foam are widely used.

On the other hand, the adhesion between the EVA foam and the PVC sheet is usually using an acrylic adhesive using an acrylic copolymer, and as related prior art, there are Patent Documents 1 and 2 and the like.

More specifically, Patent Document 1 discloses an acrylic resin composition containing an acrylic copolymer (A) having an acid value of 30 mgKOH/g or more and a weight average molecular weight of 500,000 or more, a phenol novolak-based thermosetting resin (B) and an amine-based curing agent (C). In this regard, adhesive strength and mechanical properties are exhibited by heat treatment at 180° C. for 2 hours after manufacturing the adhesive sheet.

In addition, Patent Document 2 contains 70 to 99% by weight of an alkyl (meth)acrylate having an average carbon number of an alkyl group of 2 to 14 and 1 to 30% by weight of a monoethylenically unsaturated acid copolymerizable therewith, based on the monomer mixture. Thermosetting pressure-sensitive adhesive comprising 100 parts by weight of the monomer mixture (a), 0.01 to 20 parts by weight of a split photopolymerization initiator having 3 or more peroxide groups per molecule, and 5 to 30 parts by weight of an epoxy resin (c) was proposed, and exhibits adhesive strength and heat resistance by curing at 150° C. for 2 hours.

However, in the case of conventional acrylic adhesives such as Patent Documents 1 and 2, it is essentially subjected to a process of hardening by heat treatment at a high temperature of 150° C. or higher. In this case, loss of energy, manpower, and production time due to heat treatment is inevitable. However, it was impossible to apply because the adherend was damaged by heat treatment at high temperature.

Patent Document 1: Republic of Korea Patent Publication No. 10-2019-0012227 "Adhesive composition and adhesive sheet" Patent Document 2: Republic of Korea Patent Publication No. 10-2000-0023374 "Thermosetting pressure-sensitive adhesive and its adhesive sheet"

The present invention is to solve the above problems, and by providing an acrylic adhesive that is cured at room temperature and expresses adhesive strength without a separate heat treatment process, loss of energy, manpower and production time, etc. and damage to the adherend due to conventional heat treatment It is a task to be able to realize excellent adhesion while preventing it in advance.

More specifically, the present invention is prepared by mixing a non-functional acrylic monomer, a functional group-containing acrylic monomer and a reactive acrylic monomer for adhesion promotion to have at least one polar functional group and a reactive functional group in the acrylic polymer molecular chain, and the acrylic prepared as described above By additionally mixing a crosslinking agent with the adhesive composition to form an excellent crosslinking network by interaction between the functional group and the crosslinking agent contained in the acrylic adhesive, it has curing properties even at room temperature and has excellent adhesive strength.

The present invention is an acrylic adhesive composition, characterized in that it comprises an acrylic monomer mixture comprising a non-functional acrylic monomer, a functional group-containing acrylic monomer and a reactive acrylic monomer for adhesion promotion, a polymerization initiator, an adhesion promoter and a crosslinking agent. A curable acrylic adhesive composition is used as a means to solve the problem.

More specifically, the acrylic adhesive composition comprises 92 to 99% by weight of a non-functional acrylic monomer, 0.5 to 5% by weight of a functional group-containing acrylic monomer, and 0.5 to 3% by weight of a reactive acrylic monomer for adhesion promotion 100 parts by weight With respect to the polymerization initiator, 0.05 to 3.0 parts by weight, 10 to 30 parts by weight of an adhesion promoter, and a crosslinking agent may be included.

The present invention provides an acrylic adhesive that is cured at room temperature and expresses adhesive strength without a separate heat treatment process, thereby preventing loss of energy, manpower, production time, etc. and damage to the adherend due to conventional heat treatment in advance. It works.

The present invention for achieving the above effect relates to a room temperature curable acrylic adhesive composition, and only the parts necessary for understanding the technical configuration of the present invention will be described, and the description of other parts will be omitted so as not to disturb the gist of the present invention. it should be noted that

Hereinafter, the room temperature curing type acrylic adhesive composition according to the present invention will be described in detail as follows.

The present invention is an acrylic adhesive composition comprising an acrylic monomer mixture comprising a non-functional acrylic monomer, a functional group-containing acrylic monomer and a reactive acrylic monomer for adhesion promotion, a polymerization initiator, an adhesion promoter, and a crosslinking agent. Specifically, with respect to 100 parts by weight of an acrylic monomer mixture comprising 92 to 99% by weight of a non-functional acrylic monomer, 0.5 to 5% by weight of a functional group-containing acrylic monomer, and 0.5 to 3% by weight of a reactive acrylic monomer for promoting adhesion, a polymerization initiator 0.05 to 3.0 parts by weight, 10 to 30 parts by weight of an adhesion promoter, and 0.1 to 10 parts by weight of a crosslinking agent and a crosslinking agent.

Here, the non-functional acrylic monomer is methyl (metha) acrylate, ethyl (metha) acrylate, n-butyl (meth) acrylate (n-butyl (metha) )acrylate), 2-ethylhexyl(meth)acrylate), isobonyl(metha)acrylate, lauryl(metha)acrylate acrylate) or cyclohexyl (metha) acrylate, either alone or in combination of two or more.

In addition, the functional group-containing acrylic monomer is added to have at least one polar functional group in the molecular chain of the acrylic polymer, and one having a polar functional group of any one of a hydroxyl group, an amino group, a carboxyl group, or an epoxy group in the monomer structure is used. , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, hydroxypropyl as a hydroxyl group-containing acrylic monomer hydroxypropyl methacrylate, pentaerythritol triacrylate, 2-(t-butylamino)ethyl methacrylate, 2-(t-butylamino)ethyl methacrylate as an acrylic monomer containing an amino group (N,N-diethylamino)-ethyl methacrylate (2-(n,n-diethylamino)-ethyl methacrylat), 2-diisopropylaminoethyl methacrylate, 3-dimethylamino Neopentyl acrylate (3-dimethylaminoneopentyl acrylate), a carboxyl group-containing acrylic monomer acrylic acid (acrylic acid), methacrylic acid (methacrylic acid), beta-carboxyethyl acrylate (beta-carboxyethyl acrylate), 2-sulfoethyl meta Glycidyl acrylate, glycidyl as acrylate (2-sulfoethyl methacrylate), trichloroacrylic acid, 4-vinylbenzoic acid, or an acrylic monomer containing an epoxy group It can be used alone or in combination of two or more of glycidyl methacrylate. have.

In addition, the reactive acrylic monomer for adhesion promotion is added for the purpose of adhesion promotion, 3-methacryloxypropyltrimethoxysilane, 4-methacryloxyethyl trimellitic anhydride (4-methacryloxyethyl trimellitic anhydride), vinyl-triethoxy silane, bis (2-methacryloxyethyl) phosphate (bis (2-methacryloxyethyl) phospate), or monoacryloxyethyl phosphate (monoacryloxyethyl phospate) alone or in two It can be used in combination with the above.

Here, the non-functional acrylic monomer, the functional group-containing acrylic monomer and the reactive acrylic monomer for adhesion promotion are not limited to the materials listed above, and various known non-functional acrylic monomers, functional group-containing acrylic monomers and reactive acrylics for adhesion promotion The use of monomers is possible.

On the other hand, when the content of the non-functional acrylic monomer is less than 92 wt % and the content of the functional group-containing acrylic monomer and the reactive acrylic monomer for adhesion promotion exceeds 5 wt % and 3 wt %, respectively, the reaction is caused by rapid polymerization. There is a possibility that the speed control becomes difficult and the adhesive changes into a gel phase, the content of the non-functional acrylic monomer exceeds 99 wt%, and the content of the functional group-containing acrylic monomer and the reactive acrylic monomer for adhesion promotion is relatively high. When less than 0.5% by weight, respectively, there is a fear that adhesion and curing properties may be deteriorated.

The polymerization initiator is a medium for polymerization reaction of each composition, and when the content is less than 0.05 parts by weight, the reaction rate is slow, productivity is lowered, and there is a possibility that unreacted monomers may remain in the composition. On the other hand, when it exceeds 3.0 parts by weight, it is difficult to control the reaction rate due to a rapid temperature rise, and the degree of polymerization and molecular weight are lowered, thereby reducing the cohesive force of the adhesive.

On the other hand, as the polymerization initiator, a peroxide-based polymerization initiator and an azo-based polymerization initiator may be used. Specifically, the peroxide-based polymerization initiator includes benzoyl peroxide, acetyl peroxide. , dilauryl peroxide, di-tert-butyl peroxide, cumyl hydroperoxide, and hydrogen peroxide may be used. In addition, in addition to the polymerization initiator, known acetal-based, hemiacetal-based, and redox-based polymerization initiators may be used, and as the azo-based polymerization initiator, azobisisobutyronitrile (Azobisisobutyronitrile), Azo nitrile (azo nitrile), azo ester (azo ester), azo amide (azo amide), azo amidine (azo amidine) or azo imidazoline (azo imidazoline) can be used. In addition, in addition to the polymerization initiator, well-known acetal-based, hemiacetal-based, and redox-based polymerization initiators may be used, and the use of various known polymerization initiators is not limited to those listed above. This is possible.

The adhesion promoter is added to improve adhesion, and when the content is less than 10 parts by weight, there is a fear that the effect of improving the adhesion may be insignificant, and if it exceeds 30 parts by weight, there is a risk of being uneconomical.

On the other hand, the adhesion promoter may be used alone or in combination of two or more of rosin ester-based and derivatives, terpene phenol-based or aliphatic and alicyclic petroleum-based resins, but is not necessarily limited thereto No, it is possible to use various known adhesion promoters.

The cross-linking agent is added to form an excellent cross-linking network due to the interaction between the polar functional group and the cross-linking agent. If the content is less than 0.1 parts by weight, the cross-linking network may not be properly formed at room temperature, so there is a risk of not being able to express adhesion and cohesion. And, if it exceeds 10 parts by weight, there is a fear that workability, etc. may be deteriorated due to shortening of pot life due to a rapid increase in viscosity.

Meanwhile, the crosslinking agent may be isocyanate or aziridine-based, but is not limited thereto, and various known crosslinking agents may be used.

In addition, each of the above-described compositions may be added once more to proceed with an additional reaction even after completing the process as described above.

On the other hand, in the acrylic adhesive composition, additives such as plasticizer, process oil, and acrylate oligomer may be selectively applied in consideration of the purpose, object of use, environment, etc., and these additives are known in the field of acrylic adhesive composition. As additives, a detailed description thereof will be omitted. In addition, in addition to the additives listed above, it is possible to apply various known additives.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not necessarily limited only by the following examples.

1. Preparation of acrylic adhesive

(Example 1)

70 wt% of n-butyl acrylate and 22 wt% of 2-ethylhexyl acrylate as a non-functional acrylic monomer, 5 wt% of a functional group-containing acrylic monomer acrylic acid, and a reactive acrylic monomer for adhesion promotion 3-methacryloxypropyltrimethoxy Based on 100 parts by weight of the acrylic monomer mixture consisting of 3% by weight of silane, 0.05 parts by weight of a polymerization initiator (benzoyl peroxide), 10 parts by weight of an adhesion promoter (rosin ester), and an organic solvent (ethyl acetate) at room temperature (20° C.) The mixture was prepared by mixing for about 30 minutes. Then, 30% by weight of the mixture is added to the reactor and stirring (reflux cooler, thermometer setting, nitrogen injection) is started while the temperature is raised to 80° C. After the reaction starts, the remaining 70% by weight of the mixture is dropped at the point of viscosity increase. (dropping), the viscosity was controlled by dropping the organic solvent at the point where additional bubbles were generated and the viscosity rapidly increased. And when the conversion rate reached 100%, cooling and reaction were terminated at 80° C. to room temperature, and 0.1 parts by weight of a crosslinking agent (isocyanate) was mixed thereto to prepare an acrylic adhesive.

(Example 2)

Non-functional acrylic monomer ethyl acrylate 50% by weight, n-butyl acrylate 24% by weight, butyl methacrylate 25% by weight, and functional group-containing acrylic monomer glycidyl methacrylate 0.5% by weight and reactive acrylic monomer vinyl for adhesion promotion - With respect to 100 parts by weight of the acrylic monomer mixture composed of 0.5% by weight of triethoxysilane, 3.0 parts by weight of a polymerization initiator (azobisisobutyronitrile) and 30 parts by weight of an adhesion promoter (terpene phenol), and an organic solvent (ethyl acetate) was mixed at room temperature (20° C.) for about 30 minutes to prepare a mixture. Then, 30% by weight of the mixture is added to the reactor and stirring (reflux cooler, thermometer setting, nitrogen injection) is started while the temperature is raised to 80° C. After the reaction starts, the remaining 70% by weight of the mixture is dropped at the point of viscosity increase. (dropping), the viscosity was controlled by dropping the organic solvent at the point where additional bubbles were generated and the viscosity rapidly increased. And when the conversion rate reached 100%, cooling and reaction were terminated at 80° C. to room temperature, and 10 parts by weight of a crosslinking agent (aziridine) was mixed thereto to prepare an acrylic adhesive.

(Example 3)

92 wt% of an acrylic monomer (methyl (meth)acrylate) and 5 wt% of a functional group-containing acrylic monomer (2-hydroxyethyl acrylate) and a reactive acrylic monomer for adhesion promotion (3-methacrylocpropyltrimethoxysilane) Based on 100 parts by weight of the acrylic monomer mixture consisting of 3% by weight, 0.05 parts by weight of a polymerization initiator (benzoyl peroxide), 10 parts by weight of an adhesion promoter (rosin ester), and an organic solvent (ethyl acetate) at room temperature (20° C.) about The mixture was prepared by mixing for 30 minutes. Then, 30% by weight of the mixture is added to the reactor and stirring (reflux cooler, thermometer setting, nitrogen injection) is started while the temperature is raised to 80° C. After the reaction starts, the remaining 70% by weight of the mixture is dropped at the point of viscosity increase. (dropping), the viscosity was controlled by dropping the organic solvent at the point where additional bubbles were generated and the viscosity rapidly increased. And when the conversion rate reached 100%, cooling and reaction were terminated at 80° C. to room temperature, and 0.1 parts by weight of a crosslinking agent (isocyanate) was mixed thereto to prepare an acrylic adhesive.

(Example 4)

99% by weight of an acrylic monomer (ethyl (meth)acrylate) and 0.5% by weight of a functional group-containing acrylic monomer (2-(t-butylamino)ethyl methacrylate) and a reactive acrylic monomer for adhesion promotion (4-methacryloxyethyl) With respect to 100 parts by weight of the acrylic monomer mixture consisting of 0.5% by weight of trimellitic anhydride), 3.0 parts by weight of a polymerization initiator (azobisisobutyronitrile) and 30 parts by weight of an adhesion promoter (terpene phenol), an organic solvent (ethyl acetate) ) was mixed at room temperature (20° C.) for about 30 minutes to prepare a mixture. Then, 30% by weight of the mixture is added to the reactor and stirring (reflux cooler, thermometer setting, nitrogen injection) is started while the temperature is raised to 80° C. After the reaction starts, the remaining 70% by weight of the mixture is dropped at the point of viscosity increase. (dropping), the viscosity was controlled by dropping the organic solvent at the point where additional bubbles were generated and the viscosity rapidly increased. And when the conversion rate reached 100%, cooling and reaction were terminated at 80° C. to room temperature, and 10 parts by weight of a crosslinking agent (aziridine) was mixed thereto to prepare an acrylic adhesive.

(Comparative Example 1)

It was prepared in the same manner as in Example 1, but the functional group-containing acrylic monomer was not added.

(Comparative Example 2)

It was prepared in the same manner as in Example 1, except that a reactive acrylic monomer for promoting adhesion was not added.

(Comparative Example 3)

It was prepared in the same manner as in Example 2, but the functional group-containing acrylic monomer was not added.

(Comparative Example 4)

Prepared in the same manner as in Example 2, but did not add a reactive acrylic monomer for adhesion promotion.

(Comparative Example 5)

It was prepared in the same manner as in Example 1, but no crosslinking agent was added.

(Comparative Example 6)

It was prepared in the same manner as in Example 2, but no crosslinking agent was added.

2. Evaluation of acrylic adhesives

After applying the adhesive according to the above examples and comparative examples on the fiber-reinforced sheet (combined glass fiber and PVC sheet) having a width of 20 mm, the EVA foam is laminated on the adhesive coating layer, and left for 24 hours at room temperature. The strength was evaluated. Here, the adhesive strength was evaluated by peeling at a rate of 200 ± 20 mm/min using a universal tensile tester (UTM, Zwick model 1435), and 5 adhesive specimens were measured to measure the average value, and the result was It is shown in [Table 1] and [Table 2] below.

division unit Example 1 Example 2 Example 3 Example 4 Adhesive strength kgf/2cm 0.9 0.8 0.8 0.9 adhesion state Exterior Destruction of the adherend Destruction of the adherend Destruction of the adherend Destruction of the adherend

division unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Adhesive strength kgf/2cm 0.5 0.4 0.4 0.3 0.2 0.1 adhesion state Exterior surface
peeling surface
peeling surface
peeling surface
peeling surface
peeling surface
peeling

As shown in [Table 1] and [Table 2], in Comparative Examples 1 to 4, compared to Examples 1 to 4, an acrylic adhesive was synthesized by excluding the functional group-containing acrylic monomer and the reactive acrylic monomer for adhesion promotion, and a crosslinking agent It can be seen that the adhesive strength was insufficient compared to the example even though it was added. Here, the adhesive strength of 0.8kgf/2cm or more means good adhesive strength enough to destroy the EVA foam, which is the adherend, and when the adhesive strength is 0.5 or less, only simple surface peeling occurs, which means that the adhesive strength is insufficient. Comparative Examples 5 to 6 is a case in which a crosslinking agent is not added to the acrylic adhesive prepared under the same conditions as in Examples 1 to 4, and it can be seen that the adhesive strength is 0.2 kgf/2cm or less, which is a very low value.

As described above, the room temperature curable acrylic adhesive composition according to the present invention has been described through the above preferred embodiments, and its excellence has been confirmed, but those skilled in the art can learn from the spirit and scope of the present invention described in the claims below. It will be understood that various modifications and changes can be made to the present invention without departing from it.

Claims (6)

In the acrylic adhesive composition comprising a non-functional acrylic monomer, a functional group-containing acrylic monomer and an acrylic monomer mixture comprising a reactive acrylic monomer for adhesion promotion, a polymerization initiator, an adhesion promoter and a crosslinking agent,
Based on 100 parts by weight of an acrylic monomer mixture comprising 92 to 99% by weight of non-functional acrylic monomer, 0.5 to 5% by weight of a functional group-containing acrylic monomer and 0.5 to 3% by weight of a reactive acrylic monomer for promoting adhesion, 0.05 to 3.0 parts by weight of a polymerization initiator , 10 to 30 parts by weight of adhesion promoter and 0.1 to 10 parts by weight of crosslinking agent
The non-functional acrylic monomer is methyl (metha) acrylate, ethyl (metha) acrylate, n-butyl (meth) acrylate (n-butyl (metha) acrylate) ), 2-ethylhexyl(metha)acrylate, isobonyl(metha)acrylate, lauryl(metha)acrylate , or used alone or in combination of two or more of cyclohexyl (metha) acrylate,
The functional group-containing acrylic monomer is a hydroxyl group, an amino group, a carboxyl group, or an epoxy group in the monomer structure, but uses one having a polar functional group, 2-hydroxyethyl acrylate ), 2-hydroxyethyl methacrylate, glycerol monomethacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, amino group 2-(t-butylamino)ethyl methacrylate), 2-(ene,n-diethylamino)-ethyl methacrylate (2-(n, n-diethylamino)-ethyl methacrylat), 2-diisopropylaminoethyl methacrylate, 3-dimethylaminoneopentyl acrylate, acrylic monomer containing a carboxyl group, acrylic acid (acrylic) acid), methacrylic acid, beta-carboxyethyl acrylate, 2-sulfoethyl methacrylate, trichloroacrylic acid, 4- It is used alone or in combination of two or more of glycidyl acrylate and glycidyl methacrylate as vinyl benzoic acid, or an acrylic monomer containing an epoxy group,
The reactive acrylic monomer for adhesion promotion is 3-methacryloxypropyltrimethoxysilane, 4-methacryloxyethyl trimellitic anhydride, vinyl-triethoxy silane ( Vinyl triethoxy silane), bis (2-methacryloxyethyl) phosphate (bis (2-methacryloxyethyl) phospate) or monoacryloxyethyl phosphate (monoacryloxyethyl phospate) used alone or in combination of two or more,
The polymerization initiator is used alone or in combination of two or more of peroxide-based polymerization initiators or azo-based polymerization initiators,
The adhesion promoter is used alone or in combination of two or more of rosin ester-based and derivatives, terpene phenol-based or aliphatic and alicyclic petroleum-based resins,
The crosslinking agent is an isocyanate (isocyanate) or aziridine (aziridine) type, characterized in that using a room temperature curable acrylic adhesive composition. delete delete delete delete delete