KR20200055273A - Development of a UV-curing process using a dental adhesive resin composition capable of bonding-bonding - Google Patents

Abstract

The present invention relates to a manufacturing method of a bonding-debonding adhesive bonding resin and an adhesive bonding tape and, more specifically, to a manufacturing method of a UV-curable bonding-debonding adhesive bonding resin by synthesizing a vinyl group on a resin manufactured using an acrylic monomer, and to an adhesive bonding tape. An excellent bonding-debonding process using the adhesive bonding tape is developed and provided.

Description

Development of a point adhesive resin composition capable of bonding and debonding and an ultraviolet curing process using the same {Development of a UV-curing process using a dental adhesive resin composition capable of bonding-bonding}

The present invention relates to an acrylic adhesive resin composition and a method for manufacturing a UV-curable bonding-debondable point adhesive resin using the same and a tape for adhesive bonding comprising the same. More specifically, the present invention relates to the manufacture of a highly functional point adhesive resin having excellent debonding properties even under oxygen and a tape for point adhesive using the same.

The present invention relates to a debonding point adhesive resin by ultraviolet curing, which has excellent point adhesive strength, improves the workability of the adherend fixed by the point adhesive film, and has excellent debonding property after ultraviolet curing and does not contaminate the adherend surface. It relates to a UV-curable debonding point adhesive resin. The tape can be used in the process of manufacturing and re-removing the tape using the adhesive resin, and it is used throughout the industry where cutting materials such as building materials, ITO glass, PCB substrates, and films for protecting electronic materials and other debonding are used. It is a point adhesive tape.

Since the adhesive tape containing the adhesive composition has a constant adhesive strength, it plays a role of preventing shaking and scattering when cutting the adhesive, and after the cutting process is over, each cut adhered due to a rapid decrease in adhesive strength by ultraviolet irradiation It is a functional tape that allows me to easily separate from the adhesive tape. Therefore, the adhesive tape should have a certain point adhesive strength before UV irradiation, and the adhesive strength should be reduced after UV irradiation to peel off the adhesive and do not leave the adhesive adhesive on the adhesive.

However, these adhesive tapes are made of acrylic photopolymerization, and when UV cured, they are completely cured by being blocked with oxygen in the case of the surface bonded to the adherend, but hardened by being exposed to oxygen in the case of the tape side not adhered to the adherend. In some cases, a point adhesive resin may remain on the adherend because it is not well done. In some cases, it may not be used in a process where re-coating with other adherends occurs during the process. Therefore, the present invention was developed to solve the above problems by developing a point adhesive resin that is well cured with UV light even in an exposed state in the air, and a process for blocking air in the process of use.

The present invention is to provide an ultraviolet curable bonding-debonding point adhesive resin composition using the acrylic resin after synthesis and tape it.

Another object of the present invention is to provide a bonding-debonding point adhesive resin that is well cured with ultraviolet rays even when exposed to oxygen, and is well cured with ultraviolet rays even when exposed to oxygen during re-removal after the cutting process, so that there is no adherend contamination when re-removed. It is to provide a process.

In order to achieve the above object, the present invention prepares an acrylic resin using an acrylic monomer. The acrylic resin is a OH value (hydroxy value) of 5 to 30, an acid value (acid value) of 3 to 40, a weight average molecular weight of 200,000 to 1,500,000, and a solid content of 30 to 60 parts by weight by using a commonly used acrylic monomer. It provides an acrylic resin having a characteristic value of -75 to 0 ℃ glass transition temperature.

In addition, embodiments of the present invention provides an ultraviolet curable bonding-debonding adhesive composition comprising the acrylic resin composition and comprising a photoinitiator and mercaptans.

In addition, embodiments of the present invention provides an adhesive tape comprising a UV curable bonding-debonding adhesive composition.

It also provides a nitrogen-filled space to block oxygen in the processing process.

According to the embodiments of the present invention, bonding-debonding is possible by UV curing with high adhesive strength, and an acrylic adhesive adhesive resin composition that does not leave a residual amount of residual adhesive resin on the adhesive during debonding and a tape for adhesive adhesive comprising the same Is obtained.

In addition, it provides a device capable of nitrogen filling so that UV curing can be performed well when the tape surface is exposed to the outside during processing, thereby improving process suitability.

Acrylic resin production

The acrylic resin is prepared to have an acrylic backbone structure including a hydroxy group and a carboxyl group.

The solid content of the acrylic resin is preferably 20 to 80% by weight relative to the total weight of the acrylic resin, more preferably 30 to 70% by weight.

If the solid content is less than 20% by weight, it is not preferable because there is a limitation in the thickness control and solvent selection of the point adhesive resin, and when it exceeds 80% by weight, it is difficult to control the viscosity of the point adhesive resin, and thus it is not preferable because the processability such as coating is not good. Therefore, in preparing the acrylic resin, the solid content of the acrylic resin has a range of 20 to 80% by weight, and more preferably 30 to 70% by weight.

The acrylic resin is an OH value (hydroxy value) of 5 to 30, an acid value (Acid Value) of 3 to 40, a weight average molecular weight of 200,000 to 1,500,000, and a solid content of 30 to 60 parts by weight using an acrylic monomer that is generally used. And, it is possible to synthesize an acrylic resin having a characteristic value of -75 to 0 ℃ glass transition temperature.

When the OH value (hydroxy value) of the acrylic resin is 5 or less, the synthetic space of the vinyl group is insufficient, and UV curing may be difficult. If the OH value is 30 or more, synthesis may be difficult due to the increase in viscosity of the adhesive resin, so that the OH value is It is preferred to have a range from 5 to 30.

When the acid value is 3 or less, a decrease in overall coating properties occurs due to a lack of chemical bonds during the curing reaction, and if the acid value exceeds 40, gelation of the resin may occur. Therefore, the acid value is preferably in the range of 3 to 40.

If the weight average molecular weight of the acrylic resin is 200,000 or less, the molecular weight is small, and the cohesive force of the adhesive coating film becomes weak, which may cause contamination of the adherend. If the weight average molecular weight exceeds 1,500,000, workability is limited due to the limitation of proper viscosity control of the adhesive resin. It becomes vulnerable. Therefore, the weight average molecular weight is preferably 200,000 to 1,500,000.

 If the glass transition temperature of the acrylic resin is less than 75 ° C, it is difficult to maintain the cohesive force of the point adhesive resin coating film, and it is difficult to synthesize the resin because monomer selection is not easy, and when the glass transition temperature exceeds 0 ° C, it is difficult to exhibit the adhesive properties. . Therefore, the glass transition temperature of the acrylic resin is preferably -75 ℃ to 0 ℃.

The acrylic monomer used in the acrylic resin is an acrylic acid alkyl ester such as ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, and butyl methacrylate. , Methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methyl acrylate, methyl methacrylate, vinyl acetate , Monomers containing carboxylic acid groups such as styrene, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxy butyl acrylate, 2 -It is preferable to use monomers containing hydroxy groups such as hydroxypropyl (meth) acrylate, N-methylolacrylamide, acrylamide, methacrylamide, and glycidylamide alone or in combination. In addition, lauryl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, 2-hydroxyethyl Single functional acrylates such as acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-phenoxyacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri Acrylic acid derivatives such as polyfunctional acrylates such as acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropanacrylate benzoate, 2-ethylhexyl methacrylate, and n- Single functional group methacrylates such as stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxybutyl methacrylate, 1,6-hexane Methacrylic acid derivatives such as polyfunctional methacrylates such as diol dimethacrylate, trimethylolpropane trimethacrylate and glycerin dimethacrylate, glycerin dimethacrylate hexamethylene diisocyanate, pentaerythritol triacrylate hexamethylene di It is also possible to use monomers or oligomers such as urethane acrylates such as isocyanate alone or in combination.

Preparation of UV curable adhesive resin composition

A UV-curable resin is prepared by synthesizing a vinyl group capable of UV curing on the prepared acrylic resin.

The UV-curable bonding-debonding point adhesive resin is further synthesized with a vinyl group. 3 to 20 parts by weight of 2-isocyanate ethyl methacrylate is used.

When the content of 2-isocyanate ethyl methacrylate is 3 or less, UV curing is difficult because the vinyl group is not sufficiently synthesized, and if it is 20 parts by weight or more, synthesis may be difficult due to the addition reaction of unreacted monomers that have not participated in this reaction.

The UV-curable pressure-sensitive adhesive composition may be prepared by using a curing accelerator that allows the de-bonding to be well achieved by curing the UV-curable resin thus prepared under a photoinitiator and oxygen.

The photoinitiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylano acetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p- Phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone (thioxanthone), 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylamino benzoic acid ester, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. }

In addition, curing accelerators include 1-dodecylmercaptan, 2-mercaptoethanol, 2-mercaptopropanol, thiopropylene glycol, thioglycol-conic acid, thiomaleic acid, thioglyconic acid, isooctylglycolate, and butyl mertabtopyro And propionate, butylthioglycolate, and alkylmercaptan.

Improved debonding process efficiency

In the debonding process, the UV-cured part is adhered to the adherend during UV curing, and UV curing is performed well without contacting with oxygen, but the adhesive does not disappear because curing does not occur in other parts. Due to this, there is a limitation that it cannot be used in all processes and should be used only in some processes. After the processing of the adherend was finished, the process was improved by blocking oxygen when curing the adhesive tape that was not combined with some adherends. (Drawing) Oxygen by filling nitrogen (N ₂ ) in the chamber where UV curing was performed. And the curing was performed well.

Example 1

Acrylic adhesive resin manufacturing

40 parts by weight of ethyl acetate, 30 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of normal butyl acrylate, and 2-hydroxyethyl acrylate in a reactor composed of a 1 L 5-neck flask equipped with a stirrer, water bath, thermometer, and condenser. 10 parts by weight and 5 parts by weight of acrylic acid were added and the temperature was increased to 60 ° C. under nitrogen filling. When the temperature was elevated, 0.1 parts by weight of 2,4-azobis 2,4-dimethylvaleronitrile was added as a thermal initiator, followed by thermal polymerization by uniform stirring. To the acrylic resin, 0.05 parts by weight of hydroquinone was added again, and 15 parts by weight of 2-isocyanate ethyl methacrylate was added and maintained for 6 hours to prepare a point adhesive resin.

Bonding-debonding point adhesive resin composition was prepared by adding 2 parts by weight of 1-hydroxycyclohexylphenylketone and 0.2 parts by weight of 1-dodecylmercaptene to the prepared resin.

Bonding-debonding adhesive tape manufacturing

The prepared bonding-debonding point adhesive composition was coated on a 100 micro polyethylene terephthalate film with a pressure-sensitive adhesive coating film of 25 micrometers in thickness to prepare an ultraviolet curable bonding-debonding point adhesive tape, and then attached to the SUS 304 specimen before ultraviolet irradiation The post-adhesive strength was tested, and irradiated with ultraviolet light under nitrogen filling without being adhered to SUS 304, and then adhered to the SUS 304 specimen, and then measured the adhesive strength (Table).

Example 2

Acrylic adhesive resin manufacturing

40 parts by weight of ethyl acetate, 30 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of normal butyl acrylate, and 2-hydroxyethyl acrylate in a reactor composed of a 1 L 5-neck flask equipped with a stirrer, water bath, thermometer, and condenser. 10 parts by weight and 5 parts by weight of acrylic acid were added and the temperature was increased to 60 ° C. under nitrogen filling. When the temperature was elevated, 0.1 parts by weight of 2,4-azobis 2,4-dimethylvaleronitrile was added as a thermal initiator, followed by thermal polymerization by uniform stirring. To the acrylic resin, 0.05 parts by weight of hydroquinone was added again, and 5 parts by weight of 2-isocyanate ethyl methacrylate was added and maintained for 6 hours to prepare a point adhesive resin.

Bonding-debonding point adhesive resin composition was prepared by adding 2 parts by weight of 1-hydroxycyclohexylphenylketone and 0.2 parts by weight of 1-dodecylmercaptene to the prepared resin.

Bonding-debonding adhesive tape manufacturing

The prepared bonding-debonding point adhesive composition was applied to a 100 micro polyethylene terephthalate film with a dry adhesive film thickness of 25 micro to prepare an ultraviolet curable bonding-debonding point adhesive tape, and then attached to the SUS 304 specimen, followed by ultraviolet irradiation Before and after the point adhesion was tested, and irradiated with ultraviolet light under nitrogen filling without being adhered to SUS 304, and then attached to the SUS 304 specimen, the point adhesion was measured.

Comparative Example 1

Acrylic adhesive resin manufacturing

40 parts by weight of ethyl acetate, 30 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of normal butyl acrylate, and 2-hydroxyethyl acrylate in a reactor composed of a 1 L 5-neck flask equipped with a stirrer, water bath, thermometer, and condenser. 10 parts by weight, 1 part by weight of acrylic acid was added, and the temperature was increased to 60 ° C. under nitrogen filling. When the temperature was raised, 0.1 parts by weight of 2,4-azobis 2,4dimethylvaleronitrile was added as a thermal initiator and stirred uniformly to perform thermal polymerization. To the acrylic resin, 0.05 parts by weight of hydroquinone was added again, and 15 parts by weight of 2-isocyanate ethyl methacrylate was added and maintained for 6 hours to prepare a point adhesive resin.

Bonding-debonding point adhesive resin composition was prepared by adding 2 parts by weight of 1-hydroxycyclohexylphenylketone and 0.2 parts by weight of 1-dodecylmercaptene to the prepared resin.

Bonding-debonding adhesive tape manufacturing

The prepared bonding-debonding point adhesive composition was applied to a 100 micro polyethylene terephthalate film with a dry adhesive film thickness of 25 micro to prepare an ultraviolet curable bonding-debonding point adhesive tape, and then attached to the SUS 304 specimen before ultraviolet irradiation The post-adhesive strength was tested, and irradiated with ultraviolet light under nitrogen filling without being adhered to SUS 304, and then adhered to the SUS 304 specimen, and then measured the adhesive strength (Table).

Comparative Example 2

Acrylic adhesive resin manufacturing

40 parts by weight of ethyl acetate, 30 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of normal butyl acrylate, and 2-hydroxyethyl acrylate in a reactor composed of a 1 L 5-neck flask equipped with a stirrer, water bath, thermometer, and condenser. 10 parts by weight and 5 parts by weight of acrylic acid were added and the temperature was increased to 60 ° C. under nitrogen filling. When the temperature was elevated, 0.1 parts by weight of 2,4-azobis 2,4-dimethylvaleronitrile was added as a thermal initiator, followed by thermal polymerization by uniform stirring. The acrylic resin was added again with 0.05 parts by weight of hydroquinone, and 15 parts by weight of 2-isocyanate ethyl methacrylate was added and maintained for 6 hours to prepare a point adhesive resin.

Bonding-debonding point adhesive resin composition was prepared by adding 2 parts by weight of 1-hydroxycyclohexylphenylketone to the prepared resin.

Bonding-debonding adhesive tape manufacturing

The prepared bonding-debonding point adhesive composition was applied to a 100 micro polyethylene terephthalate film with a pressure-sensitive adhesive coating film of 25 microns in thickness to prepare an ultraviolet curable bonding-debonding point adhesive tape and then attached to the SUS 304 specimen before ultraviolet irradiation The post-adhesive strength was tested, and irradiated with ultraviolet light under nitrogen filling without being adhered to SUS 304, and then adhered to the SUS 304 specimen, and then measured the adhesive strength (Table).

Comparative Example 3

Using the adhesive tape prepared in Example 1, the change of the adhesive force before and after irradiation with ultraviolet light under oxygen without nitrogen filling was measured.

Comparative Example 4

Using the adhesive tape prepared in Comparative Example 2, changes in the adhesive force before and after irradiation with ultraviolet light under oxygen without nitrogen filling were measured.

Table 1 compares the adhesive strength of the UV-curable bonding-debonding point adhesive tape in Examples and Comparative Examples.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Point adhesive force after SUS lamination
(g _f / in) 2300 2200 1200 2300 2300 2250 After SUS lamination
UV irradiation point adhesion (g _f / in) 25 90 30 25 30 30 After UV irradiation
SUS lamination point adhesion,
(g _f / in) 50 110 60 1100 800 1900

According to the measurement and comparison results in the above table, it can be seen that in Comparative Example 1, the adhesive strength of the adhesive decreased as the content of acrylic acid in the adhesive resin decreased. In Example 2, it can be seen that, compared to Example 1, the content of 2-isocyanate ethyl methacrylate is lowered, so that the point adhesive strength after UV curing in SUS lamination is slightly higher.

In Comparative Example 2, the point adhesive strength was reduced compared to Example 1 when testing the adhesive strength by laminating the surface of the adhesive resin with ultraviolet rays in a nitrogen-filled state using a tape manufactured except for 1-dodecylmercaptan and laminating it with SUS. The width was low.

In Comparative Example 3, when the adhesive surface was tested with ultraviolet rays in an oxygen state without filling nitrogen with a tape prepared using 1-dodecylmercaptan, the adhesive strength of the adhesive was reduced compared to Example 1 when laminating with SUS to test the adhesive strength. The width appeared low.

In Comparative Example 4, when using a tape manufactured except for 1-dodecylmercaptan, the surface of the point adhesive resin was exposed to oxygen without nitrogen filling, and then irradiated with UV light and then bonded to SUS to test the point adhesive strength. It can be seen that the adhesive strength of the point is almost reduced compared to that of Example 2, and in this case, it did not function as a bonding-debonding adhesive tape.

The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the present invention without departing from the technical spirit of the present invention. It will be clear to those who have the knowledge of

Claims (1)

Preparing an acrylic resin; And
Synthesizing a UV-curable vinyl group on the prepared acrylic resin to produce a UV-curable resin; Manufacturing method of a bonding-debonding point adhesive resin comprising a.