KR20050102209A - Heat-resistant acryl type adhesive - Google Patents

Abstract

The present invention relates to an acrylic adhesive, by designing an adhesive composition to have both photocurable and thermosetting properties of acrylic oligomer having a certain range of viscosity and providing a tacky adhesive by photocuring reaction to provide heat resistance by thermal curing by crosslinking reaction in a use environment. Adhesion that satisfies the adhesive at the same time, the ethylene unsaturated carboxylic acid alkyl ester monomer + ethylenically unsaturated carboxylic acid monomer alone or air of the ethylene unsaturated carboxylic acid monomer portion of 0 to 10 weight qn and the viscosity of 500 to 50,000 centipoise 100 parts by weight of coalescing oligomer (“acrylic oligomer”); 0.2 to 2 parts by weight of photoinitiator; 0.03 to 0.15 parts by weight of an unsaturated carboxylic acid alkyl ester of an alkanediol or a polyol having a hydroxy group at a sock end; 0.05 to 10 parts by weight of an ethylenically unsaturated carboxylic acid, aryl or aralkyl ester monomer, ethylene amide or ethylene amine substituted with a hydroxy group as a nucleophilic thermal reactive crosslinking component; Provided is an acrylic self-adhesive adhesive prepared by thoroughly mixing 0.5 to 4 parts of a glycidyl compound or an alkyl, aryl or aralkyl peroxide or maleic anhydride as an electrophilic thermally reactive crosslinking component and photocuring through UV light irradiation.

Description

Heat-resistant acryl type adhesive

The present invention relates to an acrylic adhesive. In particular, the present invention relates to a magnetic solvent-type acrylic adhesive that is excellent in heat resistance and adhesion, easy to store and handle, and can be variously applied.

Organic solvent-type acrylic adhesives are relatively excellent in performance such as adhesion and heat resistance, but use organic solvents that are harmful to human body. The need for products with less pollution causes an increase in the need for cleanliness for the work environment and the use environment.

Korean Patent No. 0165527 discloses an acrylic adhesive having water dispersible heat resistance instead of the organic solvent type. The patent discloses a heat-resistant acrylic adhesive prepared by emulsion polymerization by heating acrylates, carboxylic acrylics, acrylics having epoxy groups, acrylamides and acrylonitriles in batches in a watery form.

However, since the acrylic emulsion adhesive is prepared by a very complex reaction in which polymerization and crosslinking occur, it is not only simple to make an emulsion adhesive having proper properties but also insufficient heat resistance at high temperature exposure after application.

The inventors have designed an adhesive composition to have both photocurability and thermosetting properties to acrylic oligomers having a range of viscosity, and provide adhesive adhesive by photocuring reaction, thereby requiring heat resistance and adhesiveness at the same time by thermal curing by crosslinking reaction in a use environment. The present invention has been made in view of the fact that it can be used as an adhesive. The present invention is to provide a pressure-sensitive adhesive that can have a variety of modulus according to the application and a composition for producing the same. Since the adhesive adhesive of the present invention has a high adhesiveness and is stable before heating, it may be used in all fields requiring heat adhesiveness or heat resistance.

According to the present invention, an acrylic single or copolymer oligomer of an ethylene unsaturated carboxylic acid monomer monomer having an ethylene unsaturated carboxylic acid monomer portion of 0 to 10 parts by weight and a viscosity of 500 to 50,000 centipoise + an ethylenically unsaturated carboxylic acid monomer (Forward "acrylic oligomer") 100 parts by weight; 0.2 to 2 parts by weight of photoinitiator; 0.03 to 0.15 parts by weight of an unsaturated carboxylic acid alkyl ester of an alkanediol or a polyol having a hydroxy group at a sock end; 0.05 to 10 parts by weight of an ethylenically unsaturated carboxylic acid, aryl or aralkyl ester monomer, ethylene amide or ethylene amine substituted with a hydroxy group as a nucleophilic thermal reactive crosslinking component; Provided is an acrylic self-adhesive adhesive prepared by thoroughly mixing 0.5-4 parts of a glycidyl compound or an alkyl, aryl or aralkyl peroxide or maleic anhydride as an electrophilic thermally reactive crosslinking component and photocuring through UV light irradiation.

The unsaturated carboxylic acid alkyl ester monomer used in the copolymer oligomer which is the main component of the present invention is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, dimethyl fumarate, diethyl fumarate. , Dimethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate, and the like. Preferably methyl acrylate, methyl methacrylate, ethyl acrylate or ethyl methacrylate and most preferably ethyl methacrylate.

 Examples of the ethylenically unsaturated carboxylic acid monomer used in the copolymer oligomer which is the main component of the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid. Preferably acrylic acid. Acrylic acid is preferably used in the copolymerization oligomer in an amount of 1 to 6 parts by weight.

Photoinitiators are, for example, benzophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetonephenone, 1-hydroxy cyclohexylphenyl ketone, benzoin ether, benzyldimethyl ketal, thioxanthone or mixtures thereof. Preferably it is 0.3-1 weight part of 1-hydroxy cyclohexylphenyl ketones.

Unsaturated carboxylic acid alkyl esters of alkane diols or polyols having hydroxy groups at the end of the socks include HDDA (1,6-Hexanediol Diacrylate; 1,6-hexanedioldiacrylate), HD (EO) DA (1,6-Hexanediol ( ethoxylated) diacrylate; 1,6-hexanediol ethoxylated diacrylate), BDDA (1,4-Buthanediol diacrylate; 1,4-butanediol diacrylate), TEGDA (Tetraethylene glycol diacrylate); HPNDA (Hydroxy pivalic acid neopentyl glycol diacrylate; hydroxy pivalic acid neopentyl glycol diacrylate), TPGDA (tripropylene glycol diacrylate; tripropylene glycol diacrylate), DPGDA (Dipropylene glycol diacrylate; dipropylene glycol diacrylate), PEGDA (Polyethylene glycol diacrylate), PTMGDA (polyethylene glycol diacrylate), BPA (EO) DA (Bisphenol A (ethoxylated) diacrylate; bisphenol A ethoxylated diacrylate), TMPTA (trimethylolpropane triacrylate) Pantrialkylate), GPTA (Glycerin propoxylated triacrylat), PETA (pentaerythritol triacrylate), DPPA (Dipentaerythritol pentaacrylate) or DPHA (Dipentaerythritol pentaacrylate) Dipentaerythritol hexaacrylate; Dipentaerythritol hexaacrylate), and preferably 0.5 to 1.5 parts by weight of HDDA.

Monomers containing hydroxy alkyl groups as nucleophilic thermally reactive crosslinking components include 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acryl Ethylene, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate and 2-hydroxy-3-phenoxypropyl acrylate may be used, and acryl amide and ethylene amine may be used. Amides, methacrylamides, N-methylolacrylamides, N-methylolmethacrylamides, N, N-dimethylacrylamides and their corresponding amines can be used. Preferably 0.3 to 1 parts by weight of acrylamide is used.

In addition, glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, allyl glycidyl ether, etc. may be used as the glycidyl compound as the electrophilic thermally reactive crosslinking component. As the electrophilic alkyl, aryl or aralkyl peroxide, tert-butyl peroxybenzoate, di-ter-butyl peroxide, lauryl peroxide, benzoic peroxide and the like are used. Maleic anhydride may also be used. have. Preferably 1 to 3 parts by weight of glycidyl methacrylate is used.

The acrylic oligomer, photoinitiator and other additives are mixed using a mixer to form a mixed solution. The viscosity at this time is about 500 to 50,000 cps depending on the purpose of use. The mixed solution thus prepared is cured for several seconds to 10 minutes in the UV region to form a tacky adhesive.

The adhesive adhesive is applied by the adhesive at room temperature, and when exposed to a high temperature use environment, crosslinking is performed by a reaction of a thermally reactive crosslinking component, for example, a ring-opening reaction of glycidyl, thereby having heat resistance.

Hereinafter, the raw material of the present invention and the adhesive of the present invention will be described in detail with reference to Preparation Examples and Examples.

Preparation Example 1

Preparation of Acrylic Oligomer (1)

As described in Table 1, 90 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, and 0.05 parts of photoinitiator were added, placed in a reactor equipped with a high speed stirrer, and stirred under nitrogen. After stirring, photoreaction was carried out under a 365 nm wavelength to obtain an acrylic oligomer so as to have a desired viscosity (20 ° C) of 5000 to 10000 cps. The total stirring time was about 10 minutes and the light reaction time was about 1 to 5 minutes.

The average molecular weight of the oligomer thus obtained could be obtained by the following method, which was generally in agreement with the viscosity value centipoise.

<Acrylic oligomer average molecular weight measurement conditions>

It was measured using gel permission chromatography (water 2410) in a conventional manner.

Production Examples 2 to 5

Manufacture of acrylic oligomers (2,3,4,5)

After the monomers were improved in the ratios shown in Table 1, acrylic oligomers (2), (3), (4) and (5) were prepared by the same method as in Preparation Example 1.

TABLE 1

Oligomer (1) Oligomer (2) Oligomer (3) Oligomer (4) Oligomer (5) 2-ethylmethacrylate 90 94 96 98 100 Acrylic acid 10 6 4 2 0 Photoinitiator 0.05 0.05 0.1 0.05 0.2 Viscosity (cps) 6200 6250 6100 6500 6700

In the following Examples will be described with respect to the adhesive prepared using the acrylic oligomer (1, 2, 3, 4, 5) prepared above.

Example 1

An adhesive was prepared as follows using the acrylic oligomer prepared in Preparation Example 4.

100 parts of acrylic oligomers (production example 4)

IRGAQURE 184 ¹⁾ 0.5 part

HDDA ²⁾ 0.1 part

1.5 parts glycidyl methacrylate

Acrylamide0.5part

(※ ¹ above ⁾ IRGAQURE 184 is 1-hydroxy cyclohexyl phenyl ketone, and is a brand name of Shivagaigigi Specialty Co., Ltd., and ²⁾ HDDA is M200 of Miwon Corporation.)

The above is stirred using a stirrer to form a mixed solution. The viscosity at this time shows a viscosity of about 5,000 to 10,000 cps. The mixed solution thus made is uniformly applied using a laminator on a 75 μm PET film subjected to a cross-sectional release treatment. After coating, the curing reaction in the UV region (wavelength: 365 nm) for 3 minutes and then wound through a release paper to make an adhesive layer of thickness 1.5mm.

<Evaluation of Production Adhesive Layer>

The release paper LINER of the adhesive layer was removed to obtain the following physical properties.

ASKER C Hardness: 12

<Heat Resistance Experiment 1>

The sample is cut to 2 cm width and attached to a stainless steel plate (5 cm * 10 cm) (i.e. a stainless steel plate is attached to both sides of the heat sink), and then pressed once with a force of 5 kgf. After pressurizing, the test is performed at room temperature for 24 hours and then subjected to high temperature experiment. Place the stainless steel plate attached to the sample in a 100 ° C convection oven and leave for 30 minutes.

After 30 minutes, remove the stainless steel from the oven and leave for 10 minutes at room temperature. Products

Shear strength test after installation in universal tensile tester (UTM). The result is as follows.

Shear strength before high temperature treatment: 5.3kgf / in ²

Shear strength after high temperature treatment: 7.9kgf / in ²

<Heat Resistance Experiment 2>

The sample is cut to 1 cm in width and attached to a glass plate (2.5 cm * 5 cm) (the glass plate is attached to both sides of the heat dissipation pad), and then pressed once with a force of 5 kgf. Install 50g weight on one glass surface. Leave at room temperature for 1 hour. Install in a convection oven at 120 ℃ and measure the time when the additional glass surface is detached from the heat radiation pad. The result is as follows.

Measurement time: 1000 hours or more

Example 2

An adhesive layer is made using the same method as in Example 1, except that the acrylic oligomer prepared in Preparation Example 3 is used.

<Evaluation of Production Adhesive Layer>

      The release paper LINER of the adhesive layer was removed to obtain the following physical properties.

ASKER C Hardness: 15

The heat resistance test was performed as in <heat resistance test 2> of Example 1. The result was more than 1000 hours.

Example 3

An adhesive layer is made by the same method as Example 1 except for using the acrylic oligomer prepared in Preparation Example 5.

<Evaluation of Production Adhesive Layer>

The release paper LINER of the adhesive layer was removed to obtain the following physical properties.

ASKER C Hardness: 9

The heat resistance test was performed as in <heat resistance test 2> of Example 1. The result was more than 1000 hours.

<

According to the present invention, an adhesive is provided that is easy to quality control and hardened in a high temperature use environment, thereby showing a certain adhesive strength.

Claims (4)

100 parts by weight of an acrylic single or copolymer oligomer of an ethylenically unsaturated carboxylic acid alkyl ester monomer + an ethylenically unsaturated carboxylic acid monomer having an ethylene unsaturated carboxylic acid monomer portion of 0 to 10 parts by weight and a viscosity of 500 to 50,000 centipoise; 0.1 to 2 parts by weight of photoinitiator; 0.03 to 0.15 parts by weight of an unsaturated carboxylic acid alkyl ester of an alkanediol or a polyol having a hydroxy group at a sock end; 0.05 to 10 parts by weight of an ethylenically unsaturated carboxylic acid, aryl or aralkyl ester monomer substituted with a hydroxy group as a nucleophilic thermal reactive crosslinking component, ethylene amide, and ethylene amine; 0.5-3 parts of glycidyl compound or electrophilic alkyl, aryl or aralkyl peroxide or maleic anhydride are thoroughly mixed as an electrophilic thermally reactive crosslinking component, coating the paste on a release paper and irradiating UV light to photocuring reaction. Acrylic self-adhesive adhesive prepared by The method of claim 1, wherein the unsaturated carboxylic acid alkyl ester monomer used in the acrylic oligomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, dimethyl fumarate, diethyl fumarate, The ethylenically unsaturated carboxylic acid monomers selected from the group consisting of dimethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and mixtures thereof are used in the acrylic oligomer. It is selected from the group consisting of krylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and mixtures thereof; The photoinitiator is selected from the group consisting of benzophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetonephenone, 1-hydroxy cyclohexylphenyl ketone, benzoin ether, benzyldimethyl ketal, thioxanthone or mixtures thereof ; The unsaturated carboxylic acid alkyl ester of the polykan having a hydroxyl group at the alkanediol or the sock end is HDDA (1,6-Hexanediol Diacrylate; 1,6-hexanedioldiacrylate), HD (EO) DA (1,6-Hexanediol (ethoxylated) diacrylate; 1,6-hexanediol ethoxylated diacrylate), BDDA (1,4-Buthanediol diacrylate; 1,4-butanediol diacrylate), TEGDA (tetraethylene glycol diacrylate) , HPNDA (Hydroxy pivalic acid neopentyl glycol diacrylate; hydroxy pivalate neopentyl glycol diacrylate), TPGDA (tripropylene glycol diacrylate; tripropylene glycol diacrylate), DPGDA (Dipropylene glycol diacrylate), PEGDA (polyethylene glycol diacrylate), PTMGDA (polyethylene glycol diacrylate), BPA (EO) DA (Bisphenol A (ethoxylated) diacrylate; bisphenol A ethoxylated diacrylate), TMPTA (trimethylolpropane triacrylate; trimethyl Propanetrialkylate), GPTA (Glycerin propoxylated triacrylat; glycerin propoxylated triacrylate), PETA (pentaerythritol triacrylate; pentaerythritol triacrylate), DPPA (Dipentaerythritol pentaacrylate; dipentaerythritol pentaacrylate) or DPHA ( Dipentaerythritol hexaacrylate; dipentaerythritol hexaacrylate); As the nucleophilic thermoreactive crosslinking component, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacryl Latex, 3-chloro-2-hydroxypropylmethacrylate and 2-hydroxy-3-phenoxypropylacrylate, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylacrylamide, acrylamine, methacrylamine, N-methylolacrylamine or N-methylolmethacrylamine, N, N-dimethylacrylamine and the electrophilic thermally reactive crosslinking component is glycidyl Acrylate, glycidyl methacrylate, methylglycidyl acrylate, allylglycidyl ether, tert-butyl peroxybenzoate, di-ter-butyl peroxide, lauryl peroxide, benzoic peroxide or male Mountain radish The acrylic pressure-sensitive adhesive is water self. The unsaturated carboxylic acid alkyl ester monomer used in the acrylic oligomer is ethyl methacrylate, the ethylenically unsaturated carboxylic acid monomer used in the acrylic oligomer is acrylic acid, and the photoinitiator is 1-hydroxy. The hydroxy cyclohexylphenyl ketone and the alkanediol, the polyol having a hydroxy group at the sock end or their unsaturated carboxylic acid alkyl ester is HDDA and the nucleophilic thermal reactive crosslinking component is acrylamide; and the electrophilic thermal reactive crosslinking component is glycy Acrylic self-adhesive adhesive which is diacrylate. The method of claim 3, wherein the ethylenically unsaturated carboxylic acid monomer used in the acrylic oligomer is 1 to 6 parts by weight of the acrylic oligomer; The photoinitiator 0.3 to 1 part by weight; Alkanediol, the polyol which has a hydroxyl group in a sock end, or these unsaturated carboxylic acid alkyl esters are 0.05-0.2 weight part; The nucleophilic thermal reactive crosslinking component is 0.3 to 1 part by weight; and the electrophilic thermal reactive crosslinking component is 1 to 3 parts by weight of an acrylic self-adhesive adhesive.