KR102301838B1 - Polymer manufacturing composition, manufacturing method of adhesive composition, adhesive composition manufacutred thereby and adhesive film comprising same - Google Patents

Abstract

The present application relates to a composition for preparing a polymer, a method for preparing a pressure-sensitive adhesive composition, a pressure-sensitive adhesive composition prepared thereby, and an pressure-sensitive adhesive film including the same.

Description

A composition for producing a polymer, a method for producing a pressure-sensitive adhesive composition, an adhesive composition prepared thereby, and an adhesive film comprising the same

The present application relates to a composition for preparing a polymer, a method for preparing a pressure-sensitive adhesive composition, a pressure-sensitive adhesive composition prepared thereby, and an pressure-sensitive adhesive film including the same.

In the process of dicing a semiconductor wafer according to product specifications (dicing process), the semiconductor wafer is not sufficiently fixed, so that the semiconductor wafer shakes during cutting, or fragments of the semiconductor wafer scatter. is being discussed

In order to solve this problem, a method of performing a dicing process after attaching an adhesive film to the back surface of a semiconductor wafer is used. Specifically, in order to solve the above problems, a method of attaching an adhesive film to the back surface of a semiconductor wafer, fixing it to an adherend, performing a dicing process, and then irradiating ultraviolet rays to remove the adhesive film is used.

In this case, the pressure-sensitive adhesive film should be able to be easily removed from the semiconductor wafer by maintaining high adhesive strength before UV irradiation and low adhesive strength after UV irradiation.

Such an adhesive film uses an isocyanate-based compound containing an unsaturated hydrocarbon functional group in an acrylic resin containing a hydroxyl group in order to reduce the adhesive force according to UV irradiation, and through the reaction of the hydroxyl group with the unsaturated hydrocarbon functional group, the acrylic resin It is generally prepared by curing an adhesive composition comprising a curable resin to which an isocyanate-based compound is bonded.

However, the isocyanate-based compound containing the above-described unsaturated hydrocarbon functional group is toxic and not environmentally friendly, and when using it, the reaction time between the hydroxyl group and the unsaturated hydrocarbon functional group is long, so there is a problem in economic feasibility of the manufacturing process of the adhesive film.

Accordingly, without using an isocyanate-based compound, the adhesive force may be reduced according to UV irradiation, and there is a need for research on an adhesive film that can be manufactured in a short time.

Japanese Patent Laid-Open No. 2013-152963

An object of the present application is to provide a composition for preparing a polymer, a method for preparing a pressure-sensitive adhesive composition, a pressure-sensitive adhesive composition prepared according to the method, and an pressure-sensitive adhesive film including the same.

An exemplary embodiment of the present application provides a composition for preparing a polymer including an acrylate-based resin having a weight average molecular weight of 5,000 g/mol or more and 100,000 g/mol or less, an acrylate-based monomer including an alkenyl group, and an enzyme catalyst.

An exemplary embodiment of the present application includes the steps of preparing a first polymer having a weight average molecular weight of 100,000 g/mol or more and 1,000,000 g/mol or less, including a first acrylate-based resin and a first acrylate-based monomer including a photopolymerizable functional group; preparing a second polymer having a weight average molecular weight of 10,000 g/mol or more and 100,000 g/mol or less using a second acrylate-based resin, a second acrylate-based monomer including an alkenyl group, and an enzyme catalyst; And it provides a method for producing a pressure-sensitive adhesive composition comprising the step of blending the first polymer, the second polymer, and a curing agent.

In another exemplary embodiment, it is intended to provide a pressure-sensitive adhesive composition prepared according to the manufacturing method according to the exemplary embodiment of the present application.

In another exemplary embodiment, the base film; And to provide an adhesive film comprising a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive composition or a cured product thereof according to an exemplary embodiment of the present application provided on one surface of the base film.

The method for producing the pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention has the advantage of being environmentally friendly and harmless to the human body because it uses an enzyme catalyst, and has a feature that can be performed in a shorter time than the conventional method.

The adhesive film according to an exemplary embodiment of the present invention has a high adhesive strength before UV irradiation and can be used as a protective layer in the process, and after UV irradiation, the adhesive force decreases and can be removed without a residue, so it is suitable for a semiconductor wafer dicing process. .

1 is a view showing a laminated structure of an adhesive film according to an exemplary embodiment of the present application.

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

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In the case of a conventional pressure-sensitive adhesive composition prepared by reacting an unsaturated hydrocarbon with a hydroxyl group contained in an acrylic resin using an isocyanate-based compound containing an unsaturated hydrocarbon, it is confirmed that there is a problem in that it is not environmentally friendly and the production time is long. As a result of conducting several studies to solve the problem, the following invention was reached.

An exemplary embodiment of the present application provides a composition for preparing a polymer including an acrylate-based resin having a weight average molecular weight of 5,000 g/mol or more and 100,000 g/mol or less, an acrylate-based monomer including an alkenyl group, and an enzyme catalyst.

In an exemplary embodiment of the present application, the acrylate-based resin provides a composition for preparing a polymer comprising a (meth)acrylate monomer including an alkyl group and a (meth)acrylate monomer including a hydroxyl group.

In an exemplary embodiment of the present application, the composition for preparing the polymer includes 70 to 95 parts by weight of the acrylate-based resin based on 100 parts by weight of the composition for preparing the polymer; 0.5 to 25 parts by weight of the acrylate-based monomer; and 0.3 to 20 parts by weight of the enzyme catalyst.

In the case of the composition for preparing a polymer according to the present application, an acrylate-based resin having a weight average molecular weight of 5,000 g/mol or more and 100,000 g/mol or less is used to minimize steric hindrance during the enzyme-catalyzed reaction. will have

An exemplary embodiment of the present application includes the steps of preparing a first polymer having a weight average molecular weight of 100,000 g/mol or more and 1,000,000 g/mol or less, including a first acrylate-based resin and a first acrylate-based monomer including a photopolymerizable functional group; preparing a second polymer having a weight average molecular weight of 10,000 g/mol or more and 100,000 g/mol or less using a second acrylate-based resin, a second acrylate-based monomer including an alkenyl group, and an enzyme catalyst; And it provides a method for producing a pressure-sensitive adhesive composition comprising the step of blending the first polymer, the second polymer, and a curing agent.

In the exemplary embodiment of the present application, the acrylate-based resin in the composition for preparing the polymer may be the same as the second acrylate-based resin.

In the exemplary embodiment of the present application, the acrylate-based monomer in the composition for preparing the polymer may be the same as the second acrylate-based monomer.

Specifically, the present application is to react a hydroxy group and an alkenyl group included in a second polymer using a second acrylate monomer containing an alkenyl group and an enzyme catalyst. It was confirmed that it is possible to shorten the production time of the second polymer.

In the manufacturing method according to the present application, the first polymer and the second polymer are separately prepared and blended, which has a large molecular weight of the first polymer, which reduces the reactivity of the enzyme catalyst, and the photopolymerization functional group When introduced into a second polymer having a small molecular weight, the enzyme catalyst reactivity is lowered due to steric hindrance. will be. In addition, the first acrylate-based resin having a large molecular weight is used to improve adhesive strength and heat resistance, and a first acrylate-based monomer including a photopolymerizable functional group is introduced thereto.

In an exemplary embodiment of the present application, after the step of blending the first polymer, the second polymer and the curing agent, it provides a method for producing a pressure-sensitive adhesive composition further comprising the step of removing the enzyme catalyst.

In an exemplary embodiment of the present application, the enzyme catalyst may be removed after forming the second polymer.

In the case of the enzyme catalyst, it is used for the reaction and is removed by filtering later, which can be removed through a cloth mesh in a granular structure. In addition, since the removed enzyme catalyst can be reused after drying, it has the effect of reducing the cost in the process.

The weight average molecular weight is one of the average molecular weights for which the molecular weight is not uniform and the molecular weight of a certain polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

The weight average molecular weight may be measured through Gel Permeation Chromatography (GPC) analysis.

The first polymer and the second polymer refer to a product obtained by polymerizing two or more types of different units, and the polymer may have two or more types of units arranged irregularly or regularly.

The first polymer and the second polymer are a random copolymer in which monomers are mixed without regularity, a block copolymer in which blocks arranged in a certain section are repeated, or a polymer in which monomers are alternately repeated There may be an alternating copolymer (Alternating Copolymer) having a form in which the first polymer and the second polymer according to an exemplary embodiment of the present application are random copolymers, block copolymers, or alternating copolymers.

In the present specification, the unit “parts by weight” may mean a ratio of weight between each component.

As used herein, the term “monomer” may mean a unit for forming a polymer, and may mean a prepolymer composed of the same repeating unit.

In the exemplary embodiment of the present application, the first acrylate-based resin and the second acrylate-based resin may include a (meth)acrylate-based resin.

In the present specification, (meth) acrylate is meant to include both acrylate and methacrylate. The (meth)acrylate-based resin may be, for example, a copolymer of a (meth)acrylic acid ester-based monomer and a crosslinkable functional group-containing monomer.

The (meth)acrylic acid ester-based monomer is not particularly limited, but for example, an alkyl (meth)acrylate, and more specifically, a monomer having an alkyl group having 1 to 12 carbon atoms, pentyl (meth)acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethyl One or two or more of hexyl (meth)acrylate, dodecyl (meth)acrylate, and decyl (meth)acrylate may be included.

The crosslinkable functional group-containing monomer is not particularly limited, but may include, for example, one or more than one of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and a nitrogen-containing monomer.

Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate ) acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, or 2-hydroxypropylene glycol (meth)acrylate.

Examples of the carboxyl group-containing compound include (meth)acrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, 4-(meth)acryloyloxybutyric acid, acrylic acid double Sieve, itaconic acid, maleic acid, or maleic anhydride, etc. are mentioned.

Examples of the nitrogen-containing monomer include (meth)acrylonitrile, N-vinyl pyrrolidone or N-vinyl caprolactam.

At least one of vinyl acetate, styrene, and acrylonitrile may be further copolymerized with the (meth)acrylate-based resin from the viewpoint of improving other functionalities such as compatibility.

In an exemplary embodiment of the present application, the first acrylate-based resin and the second acrylate-based resin include a (meth)acrylate monomer including an alkyl group and a (meth)acrylate monomer including a hydroxyl group. A pressure-sensitive adhesive composition is provided.

In an exemplary embodiment of the present application, the first acrylate-based resin and the second acrylate-based resin may be selected from the group consisting of alkyl (meth)acrylate and hydroxyalkyl acrylate monomers.

The alkyl acrylate and alkyl methacrylate are monomers having an alkyl group having 1 to 12 carbon atoms, and pentyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylic rate, hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate and decyl (meth)acrylate One or more of them may be included.

Examples of the hydroxyalkyl acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 2 -Hydroxyethylene glycol acrylate, 2-hydroxypropylene glycol acrylate, etc. are mentioned.

In the exemplary embodiment of the present application, the first acrylate-based resin and the second acrylate-based resin may be formed of a 2-hydroxyethyl acrylate monomer and a 2-ethylhexyl (meth)acrylate monomer.

The content and composition of the first acrylate-based resin and the second acrylate-based resin may be confirmed through NMR analysis after dissolving the resin in a solvent.

In an exemplary embodiment of the present application, the first acrylate-based resin includes 60 to 90 parts by weight of the (meth)acrylate monomer including the alkyl group, based on 100 parts by weight of the first acrylate-based resin, and the hydroxyl group 5 to 40 parts by weight of a (meth)acrylate monomer.

In another exemplary embodiment, the first acrylate-based resin is based on 100 parts by weight of the first acrylate-based resin, 60 to 90 parts by weight of the (meth)acrylate monomer including the alkyl group, preferably 65 to 85 parts by weight, more preferably 70 to 85 parts by weight.

In another exemplary embodiment, the first acrylate-based resin is based on 100 parts by weight of the first acrylate-based resin, 5 to 40 parts by weight of the (meth)acrylate monomer including the hydroxyl group, preferably 10 to 30 parts by weight, more preferably 10 to 25 parts by weight.

In an exemplary embodiment of the present application, the second acrylate-based resin includes 60 to 90 parts by weight of the (meth)acrylate monomer including the alkyl group, based on 100 parts by weight of the second acrylate-based resin, and the hydroxyl group 5 to 40 parts by weight of a (meth)acrylate monomer.

In another exemplary embodiment, the second acrylate-based resin is based on 100 parts by weight of the second acrylate-based resin, 60 to 90 parts by weight of the (meth)acrylate monomer including the alkyl group, preferably 65 to 85 parts by weight, more preferably 70 to 85 parts by weight.

In another exemplary embodiment, the second acrylate-based resin is based on 100 parts by weight of the second acrylate-based resin, 5 to 40 parts by weight of the (meth)acrylate monomer including the hydroxyl group, preferably 10 to 30 parts by weight, more preferably 10 to 25 parts by weight.

When the first acrylate-based resin and the second acrylate-based resin have the above weight range, the initial adhesive strength of the pressure-sensitive adhesive may be maintained high in the future, and accordingly, in the dicing process of semiconductors, the protective film is diced. It has a feature that can protect the semiconductor by attaching it during the process.

In an exemplary embodiment of the present application, the first polymer includes 70 to 98 parts by weight of the first acrylate-based resin based on 100 parts by weight of the first polymer; and 2 to 30 parts by weight of the first acrylate-based monomer.

In another exemplary embodiment, the first polymer is 70 to 98 parts by weight, preferably 75 to 97 parts by weight, more preferably 80 parts by weight of the first acrylate-based resin based on 100 parts by weight of the first polymer. to 97 parts by weight.

In another exemplary embodiment, the first polymer is 2 to 30 parts by weight, preferably 2 to 20 parts by weight, more preferably 2.5 parts by weight of the first acrylate-based monomer based on 100 parts by weight of the first polymer. to 10 parts by weight.

In an exemplary embodiment of the present application, the second polymer may include 70 to 95 parts by weight of the second acrylate-based resin based on 100 parts by weight of the second polymer; 0.5 to 25 parts by weight of the second acrylate-based monomer; and 0.3 to 20 parts by weight of the enzyme catalyst.

In another exemplary embodiment, the second polymer, based on 100 parts by weight of the second polymer, 70 to 95 parts by weight of the second acrylate-based resin; Preferably, it may contain 75 to 95 parts by weight, more preferably 80 to 95 parts by weight.

In another exemplary embodiment, the second polymer is 0.5 to 25 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.5 parts by weight of the second acrylate-based monomer based on 100 parts by weight of the second polymer. to 5 parts by weight.

In another exemplary embodiment, the second polymer, based on 100 parts by weight of the second polymer, 0.3 to 20 parts by weight of the enzyme catalyst, preferably 0.3 to 15 parts by weight, more preferably 0.3 to 5 parts by weight may include

When the second polymer contains the above weight part, the transesterification reaction with respect to the enzyme catalyst can occur efficiently, and it has the advantage of shortening the reaction rate.

In an exemplary embodiment of the present application, the second polymer provides a method for producing a pressure-sensitive adhesive composition in an amount of 25 to 80 parts by weight based on 100 parts by weight of the first polymer.

In another exemplary embodiment, the second polymer may include 25 to 80 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the first polymer.

According to an exemplary embodiment of the present invention, the first acrylate-based monomer including the photopolymerizable functional group may have a photopolymerizable functional group bonded to the (meth)acrylate monomer.

According to an exemplary embodiment of the present invention, the photopolymerization functional group may be a hydrogen recovery type. Specifically, the photopolymerization functional group may include an ester bond (-COO-), and the ester bond may be decomposed into oxygen radicals and carbon radicals when the pressure-sensitive adhesive composition is cured.

More specifically, the oxygen radical can desorb a hydrogen radical from a (meth)acrylate monomer by decomposing a bond between hydrogen and carbon on one side of the first acrylate monomer, and a (meth)acrylate monomer including a carbon radical can form.

In addition, the oxygen radical of the photopolymerizable functional group may combine with a hydrogen radical desorbed from the first acrylate monomer to form a hydroxyl group, and when the adhesive composition is cured, the carbon radical of the photopolymerizable functional group is converted to carbon of the first acrylate monomer. It can form single bonds with radicals.

In an exemplary embodiment of the present application, the photopolymerizable functional group provides a pressure-sensitive adhesive composition comprising at least one of a benzophenone functional group, a quinone functional group, and a thioxanthone functional group.

That is, the first acrylate-based monomer including a photopolymerizable functional group may be one in which at least one of a benzophenone functional group, a quinone functional group, and a thioxanthone functional group is bonded to the acrylate monomer.

According to an exemplary embodiment of the present invention, the benzophenone functional group is benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl It may be a functional group derived from at least one compound selected from the group consisting of sulfide and 3,3'-methyl-4-methoxybenzophenone.

According to an exemplary embodiment of the present invention, the quinone functional group is quinone, anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone. It may be a functional group derived from at least one compound selected from the group consisting of.

According to an exemplary embodiment of the present invention, the thioxanthone functional group is a group consisting of thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone and isopropylthioxanthone. It may be a functional group derived from at least one compound selected from

In another exemplary embodiment, the photopolymerization functional group may be a benzophenone functional group.

In an exemplary embodiment of the present application, the first acrylate-based monomer including the photopolymerizable functional group may be benzophenone methacrylate (BPMA).

By including the first acrylate-based monomer including the photopolymerizable functional group in the first polymer, curing by UV irradiation is possible, and by introducing such an initiator into the first polymer, an initiator in a high heat resistance process Because it can prevent movement, it has the characteristic of having variable characteristics according to UV irradiation even under high temperature/high humidity/high pressure conditions.

In the exemplary embodiment of the present application, the second acrylate-based monomer including the alkenyl group may be one in which an alkenyl group is bonded to a (meth)acrylate monomer.

According to an exemplary embodiment of the present invention, the second acrylate-based monomer including an alkenyl group is vinyl (meth) acrylate, propenyl (meth) acrylate, butenyl (meth) acrylate, pentenyl (meth) It may include at least one of acrylate, hexenyl (meth)acrylate, heptenyl (meth)acrylate, octenyl (meth)acrylate, nonyl (meth)acrylate, and decanyl (meth)acrylate.

According to an exemplary embodiment of the present invention, the enzyme catalyst is Candida antarctica B lipase, Candida antarctica A lipase, Candida rugosa lipase, forsin pancreatic lipase, Pseudomonas cepacia lipase, and rhizomucor mieh lipase. may include at least one of

In an exemplary embodiment of the present application, the enzyme catalyst may be Candida Antarctica Lipase (CALB).

Since the enzyme catalyst can be reused, even if only a small amount of the enzyme catalyst is used, the transesterification reaction between the hydroxyl group and the alkenyl group can be sufficiently promoted, thereby securing economic feasibility in the manufacturing process.

The second polymer according to an exemplary embodiment of the present invention does not use an isocyanate-based compound to introduce an ethylenically unsaturated group, and uses an enzyme catalyst, so it is environmentally friendly and harmless to the human body.

In addition, the second polymer according to an exemplary embodiment of the present application has a characteristic that the reaction time is shortened by including an enzyme catalyst.

In an exemplary embodiment of the present application, the curing agent may be an NCO curing agent.

In an exemplary embodiment of the present application, a pressure-sensitive adhesive composition prepared according to the manufacturing method is provided.

In an exemplary embodiment of the present application, the pressure-sensitive adhesive composition may further include one or more selected from the group consisting of a crosslinking compound, a solvent, a dispersing agent, a photoinitiator, a thermal initiator, and a curing retardant.

According to an exemplary embodiment of the present specification, the cross-linkable compound is hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethyl Allpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene group Acidic modifications of propylene glycol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate with the number of a compound obtained by esterifying a polyhydric alcohol such as a mixture of pentaerythritol hexa(meth)acrylate (trade name: TO-2348, TO-2349, manufactured by Dong-A Synthetic Co., Ltd., Japan) with α,β-unsaturated carboxylic acid; a compound obtained by adding (meth)acrylic acid to a compound containing a glycidyl group, such as a trimethylolpropane triglycidyl ether acrylic acid adduct and a bisphenol A diglycidyl ether acrylic acid adduct; Ester compound of a compound having a hydroxyl group or an ethylenically unsaturated bond, such as a phthalic acid diester of β-hydroxyethyl (meth)acrylate and a toluene diisocyanate adduct of β-hydroxyethyl (meth)acrylate, and a polyhydric carboxylic acid , or adducts with polyisocyanates; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; and 9,9'-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, which may include one or more selected from the group consisting of, but not limited to, those known in the art. You can use common ones.

According to an exemplary embodiment of the present specification, the photoinitiator is a triazine-based compound, a biimidazole compound, an acetophenone-based compound, an O-acyloxime-based compound, a thioxanthone-based compound, a phosphine oxide-based compound, a coumarin-based compound, and a benzophenone It may be substituted with one or two or more substituents selected from the group consisting of non-based compounds.

Specifically, according to an exemplary embodiment of the present specification, the photoinitiator is 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-methyl Toxystyryl)-6-triazine, 2,4-trichloromethyl-(piflonyl)-6-triazine, 2,4-trichloromethyl-(3',4'-dimethoxyphenyl)-6 -triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propanoic acid, 2,4-trichloromethyl-(4'-ethyl ratio triazine-based compounds such as phenyl)-6-triazine or 2,4-trichloromethyl-(4'-methylbiphenyl)-6-triazine; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole or 2,2'-bis(2,3-dichlorophenyl)-4,4',5 biimidazole-based compounds such as ,5'-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxye Toxy)-phenyl (2-hydroxy)propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl-(4-methylthiophenyl)-2-mol Acetopes such as polyno-1-propan-1-one (Irgacure-907) or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (Irgacure-369) non-type compounds; O-acyloxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 manufactured by Ciba Geigy; benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone; thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chlorothioxanthone, isopropyl thioxanthone or diisopropyl thioxanthone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide or bis(2,6-dichlorobenzoyl)propyl phosphine oxide Phosphine oxide type compounds, such as; 3,3'-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin; 3-benzoyl-7-methoxy-coumarin or 10,10'-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-Cl] Coumarin-based compounds such as -benzopyrano[6,7,8-ij]-quinolizin-11-one may be used alone or two or more may be mixed, but the present invention is not limited thereto.

In addition, the thermal initiator may use one known in the art.

Furthermore, the type of the solvent is not particularly limited, and may be freely selected from general solvents known in the art used for solution polymerization.

In an exemplary embodiment of the present application, a base film; And it provides an adhesive film comprising a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive composition according to an exemplary embodiment of the present application or a cured product thereof provided on one surface of the base film.

According to an exemplary embodiment of the present invention, the pressure-sensitive adhesive sheet may be prepared by curing the pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive sheet may include a cured product of the pressure-sensitive adhesive composition.

According to an exemplary embodiment of the present invention, the pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet prepared by thermosetting the pressure-sensitive adhesive composition. However, the method of thermal curing is not particularly limited, and specifically, drying and curing for 3 minutes or more at 80° C. to 120° C., which is a temperature higher than the boiling point of the solvent, and the pressure-sensitive adhesive sheet is prepared by a method generally known in the art. It may be prepared by thermosetting the pressure-sensitive adhesive composition.

In an exemplary embodiment of the present application, there is provided an adhesive film comprising a release film on the opposite surface of the surface in contact with the base film of the adhesive sheet.

The release film is a layer for protecting a very thin pressure-sensitive adhesive sheet, and refers to a transparent layer attached to one surface of the pressure-sensitive adhesive sheet, and a film excellent in mechanical strength, thermal stability, moisture shielding property, isotropy, etc. may be used. For example, acetate-based, polyester-based, polyethersulfone-based, polycarbonate-based, polyamide-based, polyimide-based, polyolefin-based, cycloolefin-based, polyurethane-based and acrylic resin films such as triacetyl cellulose (TAC) can be used, but is not limited thereto if it is a commercially available silicone-treated release film.

In the exemplary embodiment of the present application, the base film is PET (polyethylene terephthalate), polyester, PC (polycarbonate), PI (polyimide), PAI (polyamide imide), PEN (polyethylene naphthalate), PEEK (polyether) ether ketone), polyarylate (PAR), polycylicolefin (PCO), polynorbornene, polyethersulphone (PES), and cycloolefin polymer (COP).

In another exemplary embodiment, the base film may be polyethylene terephthalate (PET) or cycloolefin polymer (COP).

In an exemplary embodiment of the present application, the thickness of the base film is 10 μm or more and 150 μm or less, preferably 15 µm or more and 100 µm or less, and more preferably 20 µm or more and 75 µm or less.

In addition, the base film is preferably transparent. The meaning that the base film is transparent here means that the light transmittance of visible light (400-700 nm) is 80% or more.

When the base film has the above range, the laminated pressure-sensitive adhesive film has the property of being able to be thinned, and it serves as a support and has excellent peel strength, and when it is rolled up in a roll form and stored and transported, the phenomenon of separation from the pressure-sensitive adhesive sheet characteristics that do not occur.

In an exemplary embodiment of the present application, the thickness of the adhesive film is 5 μm or more and 500 μm may be below.

In another exemplary embodiment, the thickness of the adhesive film is 5 μm or more and 500 μm or less, preferably 20 µm or more and 400 µm or less, more preferably 50 µm or more and 300 µm may be below.

In an exemplary embodiment of the present application, the thickness of the pressure-sensitive adhesive sheet is 3 μm or more and 50 μm may be below.

In another exemplary embodiment, the thickness of the pressure-sensitive adhesive sheet is 3 μm or more and 30 μm or less, preferably 3 µm or more and 25 µm or less, and more preferably 5 µm or more and 25 µm or less.

When the thickness of the pressure-sensitive adhesive sheet is within the above range, foreign substances do not remain when the pressure-sensitive adhesive sheet is removed, and the adhesive strength before UV irradiation is excellent.

In an exemplary embodiment of the present application, the initial adhesive force after bonding the opposite side of the surface in contact with the base film of the pressure-sensitive adhesive sheet to glass at 23° C. and 50 RH% for 1 hour is 100 gf/inch or more, and the ^{After irradiating 500mJ/cm 2} with a metal halide lamp, it provides an adhesive film having a late adhesive strength of 50 gf/inch or less at 23° C. and 50 RH%.

The adhesive force can be measured using a texture analyzer (Stable Micro Systems, Inc.) at an angle of 180° and a peeling rate of 300 mm/min. Specifically, the thickness produced by the present invention is about 25 μm. The pressure-sensitive adhesive film was cut to a width of 1 inch, and a glass substrate with an untreated surface was prepared. Then, one side of the pressure-sensitive adhesive sheet was reciprocally pressed on the glass substrate 5 times under a load of 2Kg and attached to the above angle and peeling speed. The adhesive film was peeled from a glass substrate, and adhesive force was measured, respectively.

The initial adhesive force was measured using a texture analyzer (Stable Micro Systems, Inc.) at a 180° angle and a peeling speed of 300 mm/min. Specifically, one side of the adhesive sheet was placed on a glass substrate 5 times with a load of 2Kg. After attaching by reciprocating compression, the adhesive force after standing at 23° C. and 50 RH% for 1 hour was measured.

The late adhesive strength was measured using a texture analyzer (Stable Micro Systems, Inc.) at a 180° angle and a peeling rate of 300 mm/min. Specifically, one side of the adhesive sheet was placed on a glass substrate 5 times with a load of 2Kg. After attaching by reciprocating compression, 500 mJ/cm ² was irradiated with a metal halide lamp, and the adhesive force was measured at 23° C. and 50 RH%.

In an exemplary embodiment of the present application, the initial adhesive strength of the pressure-sensitive adhesive sheet may be 100 gf/inch or more, preferably 300 gf/inch or more, and more preferably 500 gf/inch or more.

In another exemplary embodiment, the initial adhesive strength of the pressure-sensitive adhesive sheet may be 2000 gf/inch or less, preferably 1500 gf/inch or less.

In an exemplary embodiment of the present application, the late adhesive strength of the pressure-sensitive adhesive sheet may be 50 gf/inch or less, preferably 30 gf/inch or less, and more preferably 20 gf/inch or less.

In another exemplary embodiment, the adhesive sheet may have a late adhesive strength of 1 gf/inch or more, preferably 3 gf/inch or more.

The adhesive film according to an exemplary embodiment of the present invention has a high adhesive strength before UV irradiation, so it can be used as a protective layer in the process, and after UV irradiation, the adhesive force is reduced and can be removed without a residue, so it is suitable for a semiconductor wafer dicing process. .

In an exemplary embodiment of the present application, the initial adhesive force is 2 times or more and 200 times or less, preferably 5 times or more and 200 times or less, more preferably 10 times or more and 100 times or less of the later adhesive force. do.

The pressure-sensitive adhesive film according to the present application is used as a protective film, serves to protect the surface of the display in transportation and processing of the display, and has a characteristic that can be removed without leaving foreign substances through a UV curing process later.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

< manufacturing example >

1. Preparation of first polymer

manufacturing example 1-1.

91 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of 2-hydroxyethyl acrylate, and 5 parts by weight of benzophenone methacrylate were polymerized to prepare a first polymer having a weight average molecular weight of about 900,000 g/mol.

In addition, the weight average molecular weight of the first polymer is measured as a value converted to polystyrene measured by gel permeation chromatography (GPC).

manufacturing example 1-2.

In Preparation Example 1-1, with the exception of benzophenone methacrylate, 91 parts by weight of 2-ethylhexyl acrylate and 9 parts by weight of 2-hydroxyethyl acrylate were polymerized with respect to 100 parts by weight in total. A first polymer having a molecular weight of about 900,000 g/mol was prepared in the same manner as in Preparation Example 1-1.

manufacturing example 1-3.

In the preparation of the first polymer according to Preparation Example 1-2, 3 parts by weight of methacryloxyethyl isocyanate (MOI) and 0.3 parts by weight of a dibutyltin dilaurate (DBTDL, Sigma-Aldrich) catalyst A first polymer having a molecular weight of about 900,000 g/mol was prepared in the same manner as in Preparation Example 1-2 except for including parts.

manufacturing example 1-4.

In the preparation of the first polymer according to Preparation Example 1-2, 4 parts by weight of methacryloxyethyl isocyanate (MOI) and 0.4 parts by weight of a dibutyltin dilaurate (DBTDL, Sigma-Aldrich) catalyst A first polymer having a molecular weight of about 900,000 g/mol was prepared in the same manner as in Preparation Example 1-2 except for including parts.

2. Preparation of Second Polymer

manufacturing example 2-1.

Polymerization of 91 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of 2-hydroxyethyl acrylate, 0.5 parts by weight of Candida Antarctica Lipase (CALB) and 2 parts by weight of vinyl methacrylate Thus, a second polymer having a weight average molecular weight of about 50,000 g/mol was prepared.

In addition, the weight average molecular weight of the second polymer is measured as a value converted to polystyrene measured by gel permeation chromatography (GPC).

manufacturing example 2-2.

Preparation of Preparation Example 2-1, except that in Preparation Example 2-1, 0.7 parts by weight of Candida Antarctica Lipase (CALB) and 4 parts by weight of vinyl methacrylate were included A second polymer having a molecular weight of about 50,000 g/mol was prepared in the same manner as described above.

manufacturing example 2-3.

Polymerization of 91 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of 2-hydroxyethyl acrylate, 0.5 parts by weight of Candida Antarctica Lipase (CALB) and 2 parts by weight of vinyl methacrylate Thus, a second polymer having a weight average molecular weight of about 20,000 g/mol was prepared.

manufacturing example 2-4.

Polymerization of 91 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of 2-hydroxyethyl acrylate, 0.5 parts by weight of Candida Antarctica Lipase (CALB) and 2 parts by weight of vinyl methacrylate Thus, a second polymer having a weight average molecular weight of about 900,000 g/mol was prepared.

3. Preparation of pressure-sensitive adhesive composition

Information on the type of the first polymer and the second polymer included in Examples and Comparative Examples used as the pressure-sensitive adhesive composition is shown in Table 1 below, and NCO curing agent, photoinitiator and curing agent included in Examples and Comparative Examples used as the pressure-sensitive adhesive composition Information on the content of the retarder is shown in Table 2 below.

first polymer second polymer Example 1 Preparation 1-1 Preparation 2-1 Example 2 Preparation 1-1 Preparation 2-2 Example 3 Preparation 1-1 Preparation 2-3 Comparative Example 1 Preparation 1-1 - Comparative Example 2 Production Example 1-3 - Comparative Example 3 Preparation Example 1-4 - Comparative Example 4 - Preparation 2-4 Comparative Example 5 Preparation 1-2 Preparation 2-1

NCO hardener
(TKA-100) photoinitiator
(Irgacure651) curing retardant
(Acetyl acetone) Example 1 2.0 1.0 2 Example 2 1.5 1.0 2 Example 3 1.5 1.0 2 Comparative Example 1 2.0 1.0 2 Comparative Example 2 1.5 1.0 2 Comparative Example 3 2.0 1.0 2 Comparative Example 4 2.0 1.0 2 Comparative Example 5 2.0 1.0 2

The pressure-sensitive adhesive compositions of Examples 1 to 3 and Comparative Examples 1 to 5 according to Tables 1 and 2 were prepared.

After applying the pressure-sensitive adhesive composition having the composition and weight ratio of Tables 1 and 2 to PET, a heat treatment process was performed to prepare an adhesive film. The results of measuring the peel force and denaturation reaction time of Examples 1 to 3 and Comparative Examples 1 to 5 are shown in Table 3 below.

division denaturation reaction time
(hour) Adhesion of the adhesive film
(gf/in) 0 mJ/cm ²
(Initial Adhesion) 100 mJ/cm ² 200 mJ/cm ² 500 mJ/cm ²
(Later Adhesion) Example 1 5 1200 520 87 20 Example 2 5 850 450 70 15 Example 3 4 700 300 50 14 Comparative Example 1 - 1200 1250 1100 1150 Comparative Example 2 12 1000 500 200 3 Comparative Example 3 12 850 200 15 2 Comparative Example 4 reaction X 1000 800 550 200 Comparative Example 5 5 1300 650 310 75

1. Denaturation Reaction Time

In the adhesive films according to Examples 1 to 3 and Comparative Examples 1 to 5, the denaturation reaction time means the time for introducing an alkenyl group into the resin, and specifically, in Examples 1 to 3, the enzyme catalyst is a time for transesterification of the second acrylate-based monomer containing an alkenyl group with the hydroxyl group of the second acrylate-based resin, and in Comparative Examples 2 and 3, the isocyanate group of MOI and the first acrylate It means the time for the urethane reaction of the hydroxyl group of the resin.

In Table 3, “reaction X” means a case in which the introduction of an alkenyl group failed.

2. Adhesion

Samples were prepared by cutting the adhesive films according to Examples 1 to 3 and Comparative Examples 1 to 5 to a width of 1 inch, a thickness of about 25 μm, and a glass substrate having an untreated surface was prepared. Then, one side of the pressure-sensitive adhesive sheet was attached to the glass substrate by reciprocating compression 5 times under a load of 2Kg, and stored at 23° C. for 1 hour. Thereafter, the UV (light source: metal halide) irradiation conditions were changed to the attached specimen as shown in Table 3 above, and completely cured, and a peeling angle of 180° and 300 mm/ The sample was peeled from the glass substrate at a peeling rate of min, and the adhesive force of the adhesive film was measured.

As can be seen from Table 3, in Examples 1 to 3, the denaturation reaction time was 4 to 5 hours, and it was confirmed that the reaction time was shortened compared to Comparative Examples 2 and 3, which were 12 hours. That is, it was confirmed that the reaction time was shortened when an enzyme catalyst was used, compared to the case where an isocyanate group was used to introduce an alkenyl group.

In addition, the adhesive film according to Examples 1 to 3 can be confirmed that the adhesive strength is greatly reduced according to the amount of UV irradiation, and it can be confirmed that the adhesive strength is further reduced as the amount of light of the irradiated UV increases.

In Comparative Example 1, it was confirmed that the peeling force did not change even after UV irradiation because the second polymer was not used. The adhesive films according to Comparative Example 2 and Comparative Example 3 used MOI instead of vinyl methacrylate and DBTDL instead of CALB catalyst. Although it was suitable to be used for the purpose of use, there was a problem in that the efficiency of the manufacturing process was reduced as the denaturation reaction time was 12 hours, and since it contains MOI, a toxic substance known in the art, it can be confirmed that there is a safety problem in the manufacturing process of the adhesive film. there was. In Comparative Example 4, since the molecular weight of the second polymer was large, the lipase catalytic reaction did not proceed, so it was confirmed that the adhesive strength was not reduced even after UV curing. In Comparative Example 5, since there was no benzophenone methacrylate, it was confirmed that the decrease in adhesive strength due to UV curing was smaller than in Example 1, and it was not possible to crosslink the first polymer and the second polymer, which would be disadvantageous in terms of high temperature/high humidity reliability. is judged to be

In summary, when using the method for manufacturing the pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention, a high-efficiency manufacturing process can be involved, and the pressure-sensitive adhesive composition can be manufactured that is environmentally friendly and does not have safety problems, , it was confirmed that an adhesive film that can be applied to a semiconductor wafer dicing process can be prepared when the pressure-sensitive adhesive composition is used.

101: base film
102: adhesive sheet
103: adhesive film
104: release film

Claims (20)

A composition for preparing a polymer comprising an acrylate-based resin having a weight average molecular weight of 5,000 g/mol or more and 100,000 g/mol or less, an acrylate-based monomer including an alkenyl group, and an enzyme catalyst. The method according to claim 1,
The acrylate-based resin is a composition for preparing a polymer comprising a (meth)acrylate monomer including an alkyl group and a (meth)acrylate monomer including a hydroxyl group. The method according to claim 1,
The composition for preparing the polymer is based on 100 parts by weight of the composition for preparing the polymer,
70 to 95 parts by weight of the acrylate-based resin;
0.5 to 25 parts by weight of the acrylate-based monomer; and
A composition for preparing a polymer comprising 0.3 to 20 parts by weight of the enzyme catalyst. The method according to claim 1,
The enzyme catalyst is a polymer comprising at least one of Candida antarctica B lipase, Candida antarctica A lipase, Candida lugosa lipase, forsin pancreatic lipase, Pseudomonas cepaccia lipase and rhizomucor miehye lipase. composition for manufacture. Preparing a first polymer having a weight average molecular weight of 100,000 g/mol or more and 1,000,000 g/mol or less, including a first acrylate-based resin and a first acrylate-based monomer including a photopolymerizable functional group;
preparing a second polymer having a weight average molecular weight of 10,000 g/mol or more and 100,000 g/mol or less by using a second acrylate-based resin, a second acrylate-based monomer including an alkenyl group, and an enzyme catalyst; and
combining the first polymer, the second polymer and a curing agent;
A method for producing a pressure-sensitive adhesive composition comprising a. 6. The method of claim 5,
The first acrylate-based resin and the second acrylate-based resin is a method for producing a pressure-sensitive adhesive composition comprising a (meth) acrylate monomer containing an alkyl group and a (meth) acrylate monomer containing a hydroxyl group. 6. The method of claim 5,
The first polymer is based on 100 parts by weight of the first polymer
70 to 98 parts by weight of the first acrylate-based resin; and
2 to 30 parts by weight of the first acrylate-based monomer
A method for producing a pressure-sensitive adhesive composition comprising a. 6. The method of claim 5,
The second polymer, based on 100 parts by weight of the second polymer
70 to 95 parts by weight of the second acrylate-based resin;
0.5 to 25 parts by weight of the second acrylate-based monomer; and
A method for producing a pressure-sensitive adhesive composition comprising 0.3 to 20 parts by weight of the enzyme catalyst. 6. The method of claim 5,
The photopolymerization functional group is a method for producing a pressure-sensitive adhesive composition comprising at least one of a benzophenone functional group, a quinone functional group, and a thioxanthone functional group. 6. The method of claim 5,
The enzyme catalyst is Candida antarctica B lipase, Candida antarctica A lipase, Candida lugosa lipase, forsin pancreatic lipase, Pseudomonas cepaccia lipase, and Ryzomucor miehei lipase. A method for preparing the composition. 6. The method of claim 5,
The second polymer is 25 parts by weight to 80 parts by weight based on 100 parts by weight of the first polymer. 6. The method of claim 5,
After the step of combining the first polymer, the second polymer and the curing agent, the method for producing a pressure-sensitive adhesive composition further comprising the step of removing the enzyme catalyst. A pressure-sensitive adhesive composition prepared according to the method of any one of claims 5 to 12. The pressure-sensitive adhesive composition of claim 13, wherein the pressure-sensitive adhesive composition further comprises at least one selected from the group consisting of a crosslinking compound, a solvent, a dispersant, a photoinitiator, a thermal initiator, and a curing retarder. base film; and
A pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive composition of claim 13 or a cured product thereof provided on one surface of the base film;
An adhesive film comprising a. 16. The method of claim 15,
The pressure-sensitive adhesive film comprising a release film on the opposite side of the surface of the pressure-sensitive adhesive sheet in contact with the base film. The method according to claim 15, wherein the initial adhesive strength after bonding the opposite side of the surface in contact with the base film of the pressure-sensitive adhesive sheet to glass at 23°C and 50 RH% for 1 hour is 100 gf/inch or more, and then the metal halide lamp After irradiating 500mJ/cm ² with a pressure-sensitive adhesive film, the post-adhesive force at 23°C and 50 RH% is 50 gf/inch or less. The adhesive film of claim 17 , wherein the initial adhesive force is greater than or equal to 2 times and less than or equal to 200 times the later adhesive force. The method according to claim 15, wherein the adhesive film has a thickness of 5 μm or more and 500 μm. The adhesive film which is the following. The method according to claim 15, wherein the pressure-sensitive adhesive sheet has a thickness of 3 μm or more and 25 μm The adhesive film which is the following.

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