KR20220012135A - Photocurable composition and substrate for use of semiconductor process - Google Patents

Abstract

An object of the present invention is to provide a substrate for a semiconductor process comprising a photocurable composition and a coating layer capable of implementing a coating layer capable of suppressing burr generation when cutting with a high-temperature knife. The photocurable composition according to an exemplary embodiment of the present invention can implement the coating layer in which burr generation is suppressed when cutting with the high-temperature knife.

Description

Photocurable composition and substrate for semiconductor process

The present invention relates to a substrate for a semiconductor process comprising a photocurable composition and a coating layer including a cured product thereof.

A protective film in a semiconductor wafer processing process, such as a dicing process or a backside grinding process, is a laminate product having a multilayer structure including a substrate for a semiconductor process and an adhesive layer, and is used to temporarily protect a wafer during a semiconductor process.

The substrate for the semiconductor process includes a base film, and a plastic film such as polyethylene terephthalate, polyolefin, ethylene-vinyl acetate, polybutylene terephthalate, polypropylene or polyethylene is mainly used as the base film. Such a plastic film may be manufactured by melting various thermoplastic resins and applying the molten resin to a T-shaped die, suction extrusion, or calendaring method. As described above, the film manufactured by extrusion or calendaring method has advantages of excellent productivity and low price.

In general, the adhesive layer of the substrate for the semiconductor process is attached to the wafer, and the substrate for the semiconductor process is cut to correspond to the shape of the wafer with a high-temperature knife. However, when the substrate for semiconductor processing is cut with a high-temperature knife, burrs are generated in the substrate for semiconductor processing. Such a burr acts as a foreign material in the wafer grinding process, and there is a problem of causing poor fixing of the wafer and damage to the wafer.

Accordingly, there is a need for a technology capable of manufacturing a substrate for a semiconductor process in which burr generation is suppressed even when cutting with a high-temperature knife.

An object of the present invention is to provide a substrate for a semiconductor process comprising a photocurable composition and a coating layer capable of implementing a coating layer capable of suppressing burr generation when cutting with a high-temperature knife.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention is a urethane (meth)acrylate-based resin that is a reaction product of a polyalkylene carbonate-based urethane prepolymer having an isocyanate terminal group and a reactive group-containing (meth)acrylate-based compound; and at least one of an alkyl group-containing (meth)acrylate-based monomer, a cyclic alkyl group-containing (meth)acrylate-based monomer, an aromatic group-containing (meth)acrylate-based monomer, and a polar functional group-containing (meth)acrylate-based monomer and a (meth)acrylate-based monomer, wherein the polyalkylene carbonate-based urethane prepolymer is a reaction product of a polyalkylene carbonate-based polyol and an aliphatic acyclic diisocyanate-based compound, and the polyalkylene carbonate-based polyol has carbon atoms It provides a photocurable composition comprising a carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which at least one side chain of 1 to 3 is bonded.

In addition, an exemplary embodiment of the present invention, a base film; and a coating layer including a cured product of the photocurable composition.

The photocurable composition according to an exemplary embodiment of the present invention may implement a coating layer in which burr generation is suppressed when cutting with a high-temperature knife.

In addition, the substrate for a semiconductor process according to an exemplary embodiment of the present invention suppresses the generation of burrs on a cutting blade with a high-temperature knife, thereby effectively preventing damage and deformation of the wafer during wafer processing.

Effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and accompanying drawings.

1A and 1B are diagrams illustrating a substrate for a semiconductor process according to an exemplary embodiment of the present invention.

Throughout this specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

Throughout this specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, the unit "part by weight" may mean a ratio of weight between each component.

Throughout this specification, "(meth)acrylate" is used in the collective sense of acrylate and methacrylate.

Throughout this specification, terms including an ordinal number such as "first" and "second" are used for the purpose of distinguishing one element from another element, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may be referred to as a first component.

Throughout the present specification, a prepolymer may refer to a polymer in which polymerization has occurred to a certain extent between compounds, and may refer to a polymer capable of additional polymerization without reaching a completely polymerized state.

Throughout this specification, the "weight average molecular weight" and "number average molecular weight" of a compound may be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, a sample sample having a concentration of 1 wt% of the compound is prepared by putting tetrahydrofuran (THF) and a compound in a 50 ml glass bottle, and the standard sample (polystyrene, polystrene) and the sample sample are filtered (pore size). After filtration through 0.45 μm), it is injected into a GPC injector, and the molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample with the calibration curve of the standard sample. In this case, an Infinity II 1260 (Agilient Corporation) may be used as a measuring device, the flow rate may be 1.00 mL/min, and the column temperature may be set to 35.0 °C.

Throughout this specification, the viscosity of a compound (or composition) may be a value measured with a Brookfield viscometer at a corresponding temperature. Specifically, after degassing the compound (or composition) in a bubble-free state, sample 0.5 mL using a 5 mL syringe and incubate at the corresponding temperature (25 ° C) with a Brook field HB 40 spindle and measure the viscosity for 10 minutes to measure the cP value at the point in time when there is no change in viscosity.

Throughout this specification, "alkyl group" may mean including a chain hydrocarbon structure in which no unsaturated bond is present in a functional group. In addition, "cyclic alkyl group" refers to a carbon ring structure in which an unsaturated bond does not exist in a functional group. It may include, and may mean including a single ring (monocyclic ring) or multiple rings (polycyclic ring).

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

An exemplary embodiment of the present invention is a urethane (meth)acrylate-based resin that is a reaction product of a polyalkylene carbonate-based urethane prepolymer having an isocyanate terminal group and a reactive group-containing (meth)acrylate-based compound; and at least one of an alkyl group-containing (meth)acrylate-based monomer, a cyclic alkyl group-containing (meth)acrylate-based monomer, an aromatic group-containing (meth)acrylate-based monomer, and a polar functional group-containing (meth)acrylate-based monomer and a (meth)acrylate-based monomer, wherein the polyalkylene carbonate-based urethane prepolymer is a reaction product of a polyalkylene carbonate-based polyol and an aliphatic acyclic diisocyanate-based compound, and the polyalkylene carbonate-based polyol has carbon atoms It provides a photocurable composition comprising a carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which at least one side chain of 1 to 3 is bonded.

The photocurable composition according to an exemplary embodiment of the present invention may implement a coating layer in which burr generation is suppressed when cutting with a high-temperature knife.

According to an exemplary embodiment of the present invention, the urethane (meth)acrylate-based resin may include a carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which a side chain having 1 to 3 carbon atoms is bonded. The urethane (meth) acrylate-based resin includes a carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which a side chain having 1 to 3 carbon atoms is bonded, so that the urethane (meth) acrylate-based resin has a large weight average molecular weight may have, and the photocurable composition may have a relatively low viscosity. Accordingly, the photocurable composition including the urethane (meth)acrylate-based resin may have improved wetting properties and excellent coating properties. In addition, the coating layer including the cured product of the photocurable composition can effectively suppress the generation of burrs when cutting with a Coon knife.

According to an exemplary embodiment of the present invention, the polyalkylene carbonate-based polyol may include a carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which at least one side chain having 1 to 3 carbon atoms is bonded. That is, the carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms bonded to at least one side chain having 1 to 3 carbon atoms included in the urethane (meth) acrylate-based resin is derived from the polyalkylene carbonate-based polyol. can

According to an exemplary embodiment of the present invention, the polyalkylene carbonate-based polyol may include one or more carbonate repeating units. Specifically, at least one of the carbonate repeating units included in the polyalkylene carbonate-based polyol may include a carbonate repeating unit containing alkylene having 1 to 10 carbon atoms to which at least one side chain having 1 to 3 carbon atoms is bonded. By using the polyalkylene carbonate-based polyol containing the above-described carbonate repeating unit, a urethane (meth)acrylate-based resin having a large weight average molecular weight can be prepared, and the viscosity of the photocurable composition can be lowered more effectively have.

For example, the carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which at least one side chain having 1 to 3 carbon atoms is bonded may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is an alkylene having 1 to 10 carbon atoms, and R ₂ is a side chain having 1 to 3 carbon atoms.

The alkylene having 1 to 10 carbon atoms included in the carbonate repeating unit may be linear. In addition, the number of carbon atoms of the alkylene included in the carbonate repeating unit may be 3 to 8, 5 to 6, or 4 to 5. In addition, at least one side chain having 1 to 3 carbon atoms may be bonded to the main chain of the alkylene. Specifically, a methyl group, an ethyl group, or a propyl group may be bonded to the alkylene. More specifically, the carbonate repeating unit may contain an alkylene having 4 to 6 carbon atoms to which a methyl group is bonded. When the number of carbon atoms of the alkylene and the number of carbon atoms of the side chain included in the carbonate repeating unit are within the aforementioned ranges, the urethane (meth)acrylate-based resin may have a large weight average molecular weight. In addition, it is possible to effectively lower the viscosity of the photocurable composition including the urethane (meth)acrylate-based resin.

In addition, the polyalkylene carbonate-based polyol may include two or more hydroxyl groups. Specifically, the polyalkylene carbonate-based polyol may be a polyalkylene carbonate-based diol including the aforementioned carbonate repeating unit.

According to an exemplary embodiment of the present invention, the polyalkylene carbonate-based urethane prepolymer may be a reaction product of a first mixture including a polyalkylene carbonate-based polyol and an aliphatic acyclic diisocyanate-based compound. Specifically, the polyalkylene carbonate-based urethane prepolymer may be formed through a polymerization reaction between a polyalkylene carbonate-based polyol and an aliphatic acyclic diisocyanate-based compound. That is, as the reaction proceeds between the isocyanate group of the aliphatic acyclic diisocyanate-based compound and the hydroxyl group of the polyalkylene carbonate-based polyol, a urethane bond is formed, and a polyalkylene carbonate-based urethane prepolymer having an isocyanate group at the terminal is can be formed.

According to an exemplary embodiment of the present invention, the aliphatic acyclic diisocyanate-based compound may be a compound in which isocyanate groups are bonded to both ends of the main chain of the aliphatic acyclic alkylene. That is, the aliphatic acyclic diisocyanate-based compound may include a substituted or unsubstituted straight-chain alkylene main chain. In the substituted straight-chain alkylene, an alkyl group having 1 to 3 carbon atoms may be bonded to the main chain as a side chain. In addition, the aliphatic acyclic diisocyanate-based compound may not contain an aliphatic cyclic hydrocarbon and an aromatic group. By using the aliphatic acyclic diisocyanate-based compound that does not contain an aliphatic cyclic hydrocarbon and an aromatic group as a diisocyanate-based compound for forming the polyalkylene carbonate-based urethane prepolymer, a coating layer comprising a cured product of the photocurable composition The above-described burr generation can be effectively suppressed.

According to an exemplary embodiment of the present invention, the aliphatic acyclic diisocyanate-based compound may include a linear alkylene-containing diisocyanate compound having 1 to 10 carbon atoms. Specifically, the aliphatic acyclic diisocyanate-based compound may include a linear alkylene-containing diisocyanate compound having 1 to 10 carbon atoms in which an alkyl group having 1 to 3 carbon atoms is substituted or unsubstituted. More specifically, the diisocyanate compound may contain a straight-chain alkylene having 2 to 8 carbon atoms, a straight-chain alkylene having 3 to 6 carbon atoms, or a straight-chain alkylene having 5 to 6 carbon atoms. When the number of carbon atoms of the straight-chain alkylene included in the diisocyanate compound is within the aforementioned range, the urethane (meth)acrylate-based resin may have a relatively low viscosity while having a large weight average molecular weight.

According to an exemplary embodiment of the present invention, the aliphatic acyclic diisocyanate-based compound is at least one of butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and trimethylhexamethylene diisocyanate. may include By using the above-described type of the aliphatic acyclic diisocyanate-based compound, it is possible to provide a photocurable composition capable of implementing a coating layer in which burrs are suppressed when cutting with a high-temperature knife.

According to an exemplary embodiment of the present invention, the content of the aliphatic acyclic diisocyanate-based compound included in the first mixture may be 5 parts by weight or more and 13.5 parts by weight or less based on 100 parts by weight of the polyalkylene carbonate-based polyol. . Specifically, with respect to 100 parts by weight of the polyalkylene carbonate-based polyol, the content of the aliphatic acyclic diisocyanate-based compound is 7 parts by weight or more and 13.5 parts by weight or less, 10 parts by weight or more and 13 parts by weight or less, 11 parts by weight or more and 13.5 parts by weight or more. It may be less than or equal to 11.5 parts by weight, greater than or equal to 13 parts by weight, or greater than or equal to 12 parts by weight and less than or equal to 12.5 parts by weight. When the content of the aliphatic acyclic diisocyanate-based compound is within the aforementioned range, the polyalkylene carbonate-based urethane prepolymer may be stably formed. In addition, by adjusting the content of the aliphatic acyclic diisocyanate-based compound to the above-described range, the urethane (meth)acrylate-based resin having a low viscosity while having a large weight average molecular weight can be effectively formed.

According to an exemplary embodiment of the present invention, the first mixture may include a monomer for adjusting viscosity. By adding a viscosity control monomer to the first mixture, the polyalkylene carbonate-based urethane prepolymer may have an appropriate viscosity. By controlling the viscosity of the polyalkylene carbonate-based urethane prepolymer using a viscosity-controlling monomer, the polyalkylene carbonate-based urethane prepolymer can be easily polymerized with the reactive group-containing (meth)acrylate-based compound. Meanwhile, the viscosity control monomer included in the first mixture may remain in the urethane (meth)acrylate-based resin and be included in the photocurable composition. Specifically, the viscosity control monomer included in the first mixture may be a (meth)acrylate-based monomer included in the photocurable composition. That is, the viscosity control monomer included in the first mixture is included in the urethane (meth)acrylate-based resin and remains in the photocurable composition, so that the viscosity of the photocurable composition can be easily adjusted within the above-described range. .

According to an exemplary embodiment of the present invention, the urethane (meth) acrylate-based resin is a polyalkylene carbonate-based urethane prepolymer having an isocyanate terminal group and a reactive group-containing (meth) acrylate-based compound Reaction of a second mixture can be a product. That is, the urethane (meth)acrylate-based resin may be formed through a polymerization reaction between the polyalkylene carbonate-based urethane prepolymer and the reactive group-containing (meth)acrylate-based compound. Specifically, the reaction proceeds between the isocyanate group located at the end of the polyalkylene carbonate-based urethane prepolymer and the reactive group of the reactive group-containing (meth)acrylate-based compound to form the urethane (meth)acrylate-based resin have. Through this, the end of the urethane (meth) acrylate-based resin may be capped by acrylated with the reactive group-containing (meth) acrylate-based compound. In addition, the second mixture may include a monomer for adjusting the viscosity, and the monomer for adjusting the viscosity included in the second mixture may be a residue of the monomer for adjusting the viscosity included in the first mixture.

According to an exemplary embodiment of the present invention, the reactive group of the reactive group-containing (meth)acrylate-based compound may include a hydroxyl group (-OH). In terms of polymerization reactivity with the isocyanate group located at the terminal of the polyalkylene carbonate-based urethane prepolymer, a (meth)acrylate-based compound containing a hydroxyl group as a reactive group may be used. The (meth)acrylate-based compound containing a hydroxyl group as a reactive group may react with an isocyanate group positioned at the terminal of the polyalkylene carbonate-based urethane prepolymer to form a urethane bond. The urethane (meth)acrylate-based resin has a fast curing rate against UV, and the cured product of the photocurable composition including the urethane (meth)acrylate-based resin can effectively suppress the above-described burr generation.

According to an exemplary embodiment of the present invention, the reactive group-containing (meth)acrylate-based compound may not contain a carboxyl group. That is, the reactive group-containing (meth)acrylate-based compound may not contain a carboxyl group as a reactive group. When the reactive group-containing (meth)acrylate-based compound contains a carboxyl group as a reactive group, the reactivity with the isocyanate group positioned at the terminal of the polyalkylene carbonate-based urethane prepolymer is poor, and the urethane (meth)acrylate-based resin It may not be easy to form In addition, when the reactive group-containing (meth)acrylate-based compound contains a carboxyl group, there may be a problem in that the burr suppression performance of the coating layer including the cured product of the photocurable composition is lowered.

Therefore, according to an exemplary embodiment of the present invention, the urethane (meth)acrylate-based resin can be easily formed by using a (meth)acrylate-based compound that does not contain a carboxyl group as a reactive group. In addition, it is possible to provide a photocurable composition capable of forming a coating layer capable of effectively suppressing burr generation when cutting with a high-temperature knife.

According to an exemplary embodiment of the present invention, the reactive group-containing (meth)acrylate-based compound may contain alkylene having 4 or less carbon atoms. Specifically, the reactive group-containing (meth)acrylate-based compound is hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acryl It may include at least one of rates. The photocurable composition comprising a reactive group-containing (meth)acrylate-based compound having an alkylene having 4 or less carbon atoms and the urethane (meth)acrylate-based resin derived from the polyalkylene carbonate-based urethane prepolymer has a coatability Excellent, it is possible to implement a coating layer with excellent burr generation suppression performance.

According to an exemplary embodiment of the present invention, the content of the reactive group-containing (meth)acrylate-based compound included in the second mixture is 1 part by weight or more and 10 parts by weight based on 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer. may be less than or equal to Specifically, with respect to 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer, the content of the reactive group-containing (meth)acrylate-based compound is 1.5 parts by weight or more and 8.5 parts by weight or less, 2 parts by weight or more and 7 parts by weight or less, 3.5 6.5 parts by weight or more, 1 part by weight or more and 6 parts by weight or less, 1.5 parts by weight or more and 5.5 parts by weight or less, 2 parts by weight or more and 5 parts by weight or less, 2 parts by weight or more and 4.5 parts by weight or more, 3 parts by weight or more and 10 parts by weight parts by weight or less, 3.2 parts by weight or more and 8.5 parts by weight or less, 3.5 parts by weight or more and 7.5 parts by weight or less, 3.7 parts by weight or more and 7 parts by weight or less, or 4 parts by weight or more and 6.5 parts by weight or less.

By adjusting the content of the reactive group-containing (meth)acrylate-based compound to the above-described range, the burr suppression performance and mechanical properties of the coating layer including the cured product of the photocurable composition can be further improved. In addition, when the content of the reactive group-containing (meth)acrylate-based compound is within the aforementioned range, it is possible to suppress a decrease in coatability of the photocurable composition.

According to an exemplary embodiment of the present invention, the weight average molecular weight of the urethane (meth)acrylate-based resin may be 40,000 g/mol or more. Specifically, the weight average molecular weight of the urethane (meth) acrylate-based resin may be 40,000 g/mol or more and 80,000 g/mol or less. More specifically, the weight average molecular weight of the urethane (meth) acrylate-based resin is 40,000 g/mol or more and 70,000 g/mol or less, 40,000 g/mol or more and 60,000 g/mol or less, 40,000 g/mol or more and 50,000 g/mol or less , 40,000 g/mol or more and 45,000 g/mol or less, or 46,000 g/mol or more and 50,000 g/mol or less.

When the weight average molecular weight of the urethane (meth)acrylate-based resin is within the above range, the photocurable composition may implement a coating layer with improved burr generation suppression performance and mechanical properties. In addition, by adjusting the weight average molecular weight of the urethane (meth) acrylate-based resin to the above-described range, it is possible to suppress a decrease in the coatability of the photocurable composition.

According to an exemplary embodiment of the present invention, the content of the urethane (meth) acrylate-based resin may be 15 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the photocurable composition. Specifically, based on 100 parts by weight of the photocurable composition, the content of the urethane (meth)acrylate-based resin is 18 parts by weight or more and 38 parts by weight or less, 20 parts by weight or more and 35 parts by weight or less, 25 parts by weight or more and 30 parts by weight. 15 parts by weight or more and 35 parts by weight or less, 17.5 parts by weight or more and 32.5 parts by weight or less, 20 parts by weight or more and 30 parts by weight or less, 22.5 parts by weight or more and 27.5 parts by weight or less, 20 parts by weight or more and 40 parts by weight or less, 23 parts by weight It may be 37 parts by weight or more, 25 parts by weight or more and 33 parts by weight or less, or 27 parts by weight or more and 30 parts by weight or less. When the content of the urethane (meth)acrylate-based resin is within the aforementioned range, the photocurable composition may have excellent coatability. In addition, by adjusting the content of the urethane (meth) acrylate-based resin to the above-described range, it is possible to further improve the burr generation suppression performance of the coating layer.

According to an exemplary embodiment of the present invention, the photocurable composition may include the (meth)acrylate-based monomer. The (meth)acrylate-based monomer may control the viscosity of the photocurable composition and participate in a photocuring reaction of the photocurable composition to be described later.

According to an exemplary embodiment of the present invention, the (meth) acrylate-based monomer is an alkyl group-containing (meth) acrylate-based monomer, a cyclic alkyl group-containing (meth) acrylate-based monomer, and an aromatic group-containing (meth) acrylate-based monomer , and may include at least one of a polar functional group-containing (meth)acrylate-based monomer. Specifically, the (meth)acrylate-based monomer may include the alkyl group-containing (meth)acrylate-based monomer. In addition, the (meth)acrylate-based monomer may include the alkyl group-containing (meth)acrylate-based monomer and the polar functional group-containing (meth)acrylate-based monomer. In addition, the (meth)acrylate-based monomer may include the cyclic alkyl group-containing (meth)acrylate-based monomer and the polar functional group-containing (meth)acrylate-based monomer. In addition, the (meth)acrylate-based monomer includes the alkyl group-containing (meth)acrylate-based monomer, the cyclic alkyl group-containing (meth)acrylate-based monomer, the aromatic group-containing (meth)acrylate-based monomer, and the polar functional group-containing ( It may include a meth)acrylate-based monomer.

According to an exemplary embodiment of the present invention, the content of the monomer of the (meth) acrylate-based monomer may be 200 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the urethane (meth) acrylate-based resin. Specifically, with respect to 100 parts by weight of the urethane (meth)acrylate-based resin, the content of the monomer of the (meth)acrylate-based monomer is 250 parts by weight or more and 480 parts by weight or less, 270 parts by weight or more and 450 parts by weight or less, or It may be 300 parts by weight or more and 435 parts by weight or less.

By adjusting the content of the (meth)acrylate-based monomer to the above-mentioned range, the viscosity of the photocurable composition can be easily adjusted within the range to be described later. In addition, when the content of the (meth) acrylate-based monomer satisfies the above-mentioned range, it is possible to improve the coatability of the photocurable composition, and effectively improve the surface quality of the coating layer manufactured using the photocurable composition can do it

According to an exemplary embodiment of the present invention, the (meth)acrylate-based monomer may include the alkyl group-containing (meth)acrylate-based monomer. Specifically, the alkyl group-containing (meth) acrylate-based monomer is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, It may include at least one of n-octyl-5-(meth)acrylate and isooctyl (meth)acrylate.

According to an exemplary embodiment of the present invention, the content of the alkyl group-containing (meth)acrylate-based monomer included in the (meth)acrylate-based monomer is 10 parts by weight based on 100 parts by weight of the urethane (meth)acrylate-based resin. It may be more than 400 parts by weight or less. Specifically, with respect to 100 parts by weight of the urethane (meth)acrylate-based resin, the content of the alkyl group-containing (meth)acrylate-based monomer is 15 parts by weight or more and 380 parts by weight or less, 20 parts by weight or more and 360 parts by weight or less, 25 300 parts by weight or more, 10 parts by weight or more and 300 parts by weight or less, 15 parts by weight or more and 280 parts by weight or less, 20 parts by weight or more and 250 parts by weight or less, 10 parts by weight or more and 50 parts by weight or less, 15 parts by weight or more and 40 parts by weight parts by weight or less, 20 parts by weight or more and 30 parts by weight or less, 200 parts by weight or more and 400 parts by weight or less, 200 parts by weight or more and 380 parts by weight or less, or 220 parts by weight or more and 360 parts by weight or less.

By adjusting the content of the alkyl group-containing (meth)acrylate-based monomer to the above-described range, the viscosity of the photocurable composition may be appropriately adjusted to improve wettability, thereby further improving coating properties. In addition, when the content of the alkyl group-containing (meth) acrylate-based monomer is within the above range, it is possible to improve the burr suppression performance and mechanical properties of the coating layer including the cured product of the photocurable composition. On the other hand, as described above, the (meth)acrylate-based monomer containing the alkyl group included in the (meth)acrylate-based monomer may be one in which the viscosity control monomer included in the first mixture remains.

According to an exemplary embodiment of the present invention, the (meth)acrylate-based monomer may include the cyclic alkyl group-containing (meth)acrylate-based monomer. The cyclic alkyl group-containing (meth)acrylate-based monomer is at least one of isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate and trimethylcyclohexyl (meth)acrylate may contain one.

According to an exemplary embodiment of the present invention, the content of the cyclic alkyl group-containing (meth)acrylate-based monomer may be 100 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the urethane (meth)acrylate-based resin. Specifically, with respect to 100 parts by weight of the urethane (meth)acrylate-based resin, the content of the cyclic alkyl group-containing (meth)acrylate-based monomer is 115 parts by weight or more and 280 parts by weight or less, 130 parts by weight or more and 250 parts by weight or less. , 100 parts by weight or more and 250 parts by weight or less, 110 parts by weight or more and 240 parts by weight or more, 120 parts by weight or more and 230 parts by weight or less, 130 parts by weight or more and 220 parts by weight or less, 200 parts by weight or more and 300 parts by weight or more, 200 parts by weight or more It may be 275 parts by weight or less, or 200 parts by weight or more and 250 parts by weight or less.

By adjusting the content of the cyclic alkyl group-containing (meth)acrylate-based monomer to the above-mentioned range, it is possible to effectively improve the coating property by controlling the viscosity of the photocurable composition, and to effectively improve the burr suppression performance of the coating layer. can On the other hand, as described above, the cyclic alkyl group-containing (meth)acrylate-based monomer included in the (meth)acrylate-based monomer may be one in which the viscosity control monomer included in the first mixture remains.

According to an exemplary embodiment of the present invention, the (meth)acrylate-based monomer may include the aromatic group-containing (meth)acrylate-based monomer. The aromatic group-containing (meth)acrylate-based monomer is phenylbenzyl (meth)acrylate, phenylthioethyl (meth)acrylate, O-phenylphenoxyethyl (meth)acrylate and naphthylthioethyl (meth)acrylate may include at least one of

According to an exemplary embodiment of the present invention, the content of the aromatic group-containing (meth)acrylate-based monomer may be 50 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the urethane (meth)acrylate-based resin. Specifically, with respect to 100 parts by weight of the urethane (meth)acrylate-based resin, the content of the aromatic group-containing (meth)acrylate-based monomer is 60 parts by weight or more and 95 parts by weight or less, 65 parts by weight or more and 90 parts by weight or less, 50 parts by weight or more and 75 parts by weight or less, 55 parts by weight or more and 70 parts by weight or less, 60 parts by weight or more and 65 parts by weight or less, 65 parts by weight or more and 100 parts by weight or less, or 67.5 parts by weight or more and 90 parts by weight or less.

When the content of the aromatic group-containing (meth)acrylate-based monomer is within the aforementioned range, the wetting properties of the photocurable composition may be improved, and mechanical properties of the cured product of the photocurable composition may be improved. On the other hand, as described above, the aromatic group-containing (meth)acrylate-based monomer included in the (meth)acrylate-based monomer may be one in which the viscosity control monomer included in the first mixture remains.

According to an exemplary embodiment of the present invention, the (meth)acrylate-based monomer may include the polar functional group-containing (meth)acrylate-based monomer. The polar functional group-containing (meth)acrylate-based monomer may contain a hydroxyl group as a polar functional group. Specifically, the polar functional group-containing (meth)acrylate-based monomer is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- Hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethyleneglycol (meth)acrylate, 2-hydroxypropyleneglycol (meth)acrylate, and 2-hydroxy- and at least one of 3-phenoxy propyl (meth)acrylate.

According to an exemplary embodiment of the present invention, the content of the polar functional group-containing (meth)acrylate-based monomer may be 50 parts by weight or more and 110 parts by weight or less based on 100 parts by weight of the urethane (meth)acrylate-based resin. Specifically, with respect to 100 parts by weight of the urethane (meth)acrylate-based resin, the content of the polar functional group-containing (meth)acrylate-based monomer is 65 parts by weight or more and 110 parts by weight or less, 80 parts by weight or more and 110 parts by weight or less, 50 parts by weight or more and 100 parts by weight or less, 60 parts by weight or more and 95 parts by weight or less, 70 parts by weight or more and 90 parts by weight or less, 80 parts by weight or more and 85 parts by weight or less, 90 parts by weight or more and 110 parts by weight or less, 95 parts by weight or more 110 It may be less than or equal to 100 parts by weight, or 100 parts by weight or more and 110 parts by weight or less.

By adjusting the content of the polar functional group-containing (meth)acrylate-based monomer to the above-described range, the wetting and coating properties of the photocurable composition can be improved, and the burr suppression performance of the cured product of the photocurable composition can be effectively improved can be improved On the other hand, as described above, the (meth)acrylate-based monomer containing the polar functional group included in the (meth)acrylate-based monomer may be one in which the viscosity control monomer included in the first mixture remains.

According to an exemplary embodiment of the present invention, the photocurable composition may include a photoinitiator. As the photoinitiator, a photoinitiator used in the art may be employed without limitation. For example, at least one of HP-8 (Miwon Specialty), Irgacure#651 (BASF), Irgacure#1173 (BASF), and CP-4 (Irgacure#184) may be used as the photoinitiator, but the photoinitiator It does not limit the type of

According to an exemplary embodiment of the present invention, the content of the photoinitiator may be 0.2 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the urethane (meth)acrylate-based resin. Specifically, with respect to 100 parts by weight of the urethane (meth)acrylate-based resin, the content of the photoinitiator is 0.2 parts by weight or more and 50 parts by weight or less, 0.2 parts by weight or more and 40 parts by weight or less, 0.2 parts by weight or more and 30 parts by weight or less, 0.2 parts by weight or more and 15 parts by weight or less, 0.2 parts by weight or more and 7.5 parts by weight or less, 0.2 parts by weight or more and 3.5 parts by weight or less, 0.2 parts by weight or more and 1 part by weight or less, or 0.4 parts by weight or more and 0.6 parts by weight or less. By adjusting the content of the photoinitiator to the above-mentioned range, the photocuring reaction of the photocurable composition can be effectively performed.

According to an exemplary embodiment of the present invention, the viscosity of the photocurable composition may be 2,000 cP or less. Specifically, the viscosity of the photocurable composition at 25° C. may be 1,000 cP or more and 2,000 cP or less, 1,200 cP or more and 2,000 cP or less, 1,400 cP or more and 2,000 cP or less, 1,600 cP or more and 2,000 cP or less, or 1,800 cP or more and 2,000 cP or less. . As described above, the viscosity of the photocurable composition at 25° C. may be a value measured with a Brookfield HB 40 spindle. The photocurable composition having a viscosity at 25° C. that satisfies the above range has excellent coatability, and may have excellent surface quality of a coating layer including a coating film of the photocurable composition and a cured product thereof.

An exemplary embodiment of the present invention is a base film; and a coating layer including a cured product of the photocurable composition.

The substrate for semiconductor processing according to an exemplary embodiment of the present invention suppresses generation of burrs on a cutting blade with a high-temperature knife, thereby effectively preventing damage and deformation of the wafer during wafer processing. As described above, since the coating layer including the cured product of the photocurable composition can effectively suppress burr generation when cutting with a high-temperature knife, the substrate for the semiconductor process is subjected to a back grinding process or a dicing (back grinding) process. It can be easily applied to a semiconductor process such as a dicing process.

1A and 1B are diagrams illustrating a substrate for a semiconductor process according to an exemplary embodiment of the present invention.

Referring to FIG. 1A , a substrate 100 for a semiconductor process according to an exemplary embodiment of the present invention may include a base film 10 and a coating layer 20 provided on one surface of the base film 10 . In this case, the coating layer includes a cured product of the above-described photocurable composition.

According to an exemplary embodiment of the present invention, the base film may be a base film used in the art. For example, the base film may be a polyethylene terephthalate film, a polyolefin film, an ethylene-vinyl acetate film, a polybutylene terephthalate film, a polypropylene film, or a polyethylene film, but the type of the base film is not limited.

According to an exemplary embodiment of the present invention, the thickness of the base film may be 10 μm or more and 100 μm or less. Specifically, the thickness of the base film is 20 μm or more and 80 μm or less, 40 μm or more 60 μm or less, 10 μm or more and 70 μm or less, 15 μm or more and 65 μm or less, 25 μm or more and 62.5 μm or less, 30 μm or more and 57 μm or less. , 35 μm or more and 55 μm or less, 45 μm or more 50 μm or less, 40 μm or more 100 μm or less, 42.5 μm or more and 75 μm or less, 45 μm or more and 72.5 μm or less, or 50 μm or more and 65 μm or less. When the thickness of the base film is within the above range, the substrate for semiconductor processing having excellent mechanical properties can be implemented.

According to an exemplary embodiment of the present invention, the photocurable composition is applied on the base film, and the photocurable composition is photocured to form a coating layer on the base film. That is, the coating layer may be provided on the base film without a bonding film or an adhesive.

According to an exemplary embodiment of the present invention, using a UV lamp having a wavelength value of 300 nm or more and 400 nm or less, by irradiating with a light amount of 1.0 J/cm ² to 1.5 J/cm ² It is possible to cure the photocurable composition have.

According to an exemplary embodiment of the present invention, the thickness of the coating layer may be 10 μm or more and 100 μm or less. Specifically. The thickness of the coating layer is 15 μm or more and 85 μm or less, 20 μm or more 75 μm or less, 25 μm or more 70 μm or less, 30 μm or more 65 μm or less, 35 μm or more 60 μm, 40 μm or more 55 μm or less, 45 μm or more 50 μm or less, 48 μm or more and 50 μm or less, 49 μm or more and 51 μm or less, or 53 μm or more and 55 μm or less. By controlling the thickness of the coating layer in the above-described range, the mechanical properties of the coating layer can be further improved.

Referring to FIG. 1B , a substrate 100 for a semiconductor process according to an exemplary embodiment of the present invention includes a base film 10 , a coating layer 20 provided on one surface of the base film 10 , and the coating layer 20 . It may include a hard coating layer 30 provided on one surface of the. In this case, the coating layer 20 includes a cured product of the above-described photocurable composition.

According to an exemplary embodiment of the present invention, the hard coating layer may be a hard coating layer used in the art. For example, the hard coating layer may include a cured product of the hard coating layer composition including a solvent, a light (UV) curable resin, a tack-free additive, and a photoinitiator.

According to an exemplary embodiment of the present invention, the thickness of the hard coating layer may be 0.5 μm or more and 5 μm or less. When the thickness of the hard coating layer is within the aforementioned range, durability and mechanical properties of the substrate for the semiconductor process may be further improved.

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.

Hereinafter, examples will be given to describe the present invention in detail.

Example 1

Preparation of photocurable composition

Nipollan 963 (Tosoh Corporation) as a polyalkylene carbonate-based polyol containing a carbonate repeating unit containing pentylene to which a methyl group is bonded as a side chain in a 5-neck 2L reactor, and trimethylhexamethylene diisocyanate as an aliphatic acyclic diisocyanate-based compound (TMDI; Evonik) and isobornyl acrylate (IBOA, Solay) were added and mixed to prepare a first mixture. At this time, based on 100 parts by weight of Nipollan 963, the content of TMDI was 12 parts by weight.

Thereafter, the temperature of the first mixture is maintained at 65° C., 50 ppm of dibutyltin dilaurate (DBTDL), a tin-based catalyst, is added to induce an exothermic reaction, and polyalkylene carbonate having an isocyanate end group. A urethane-based prepolymer was prepared.

Thereafter, a second mixture is prepared by mixing the prepared polyalkylene carbonate-based urethane prepolymer and 2-hydroxyethyl methacrylate (2-HEMA, Japan Catalyst), which is a reactive group-containing (meth)acrylate-based compound, By confirming that the NCO peak of 2250 cm ^-1 disappeared by Fourier-transform infrared spectroscopy (FT-IR), a urethane (meth)acrylate-based resin was prepared. At this time, the content of 2-HEMA was 5.8 parts by weight based on 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer.

Then, 2-ethylhexyl acrylate (2-EHA), O-phenylphenoxyethyl acrylate (OPPEA; M1142, Miwon Specialty Co., Ltd.), 2-hydroxyethyl acrylate to the prepared urethane (meth) acrylate-based resin (2-HEA) and Irgacure#651 (BASF) as a photoinitiator were mixed to prepare a photocurable composition.

At this time, based on 100 parts by weight of the photocurable composition, the content of the urethane (meth)acrylate-based resin was 25 parts by weight. In addition, based on 100 parts by weight of the urethane (meth)acrylate-based resin, the content of IBOA is 132 parts by weight, the content of 2-EHA is 20 parts by weight, the content of OPPEA is 68 parts by weight, and the content of 2-HEA is 80 parts by weight Part, the content of the photoinitiator was 0.4 parts by weight.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 47,800 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,910 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Manufacturing of substrates for semiconductor processes

Then, on the PET base film having a thickness of about 50 μm, the prepared photocurable composition was applied using a slot die. Thereafter, the photocurable composition was cured by irradiating a total amount of light of 1.5 J/cm ² using a UV lamp having a wavelength of 340 nm under nitrogen condition. Through this, a substrate for a semiconductor process in which a coating layer having a thickness of about 53 μm was formed on a PET substrate film was prepared.

Example 2

In Example 1, based on 100 parts by weight of Nippollan 963, the content of TMDI was adjusted to 11.6 parts by weight, and the content of 2-HEMA was adjusted to 5.82 parts by weight with respect to 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer. Except that, a urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1.

In addition, the content of the urethane (meth)acrylate-based resin is adjusted to 19 parts by weight based on 100 parts by weight of the photocurable composition, and the content of IBOA is adjusted to 205 parts by weight, 2- based on 100 parts by weight of the urethane (meth)acrylate-based resin In the same manner as in Example 1, except that the content of EHA was adjusted to 26 parts by weight, the content of OPPEA was adjusted to 89 parts by weight, the content of 2-HEA was adjusted to 105 parts by weight, and the content of the photoinitiator was adjusted to 0.5 parts by weight, Compositions and substrates for semiconductor processing were prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 79,900 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,980 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Example 3

In Example 1, based on 100 parts by weight of Nipollan 963, the content of TMDI was adjusted to 12.6 parts by weight, and the content of 2-HEMA was adjusted to 5.77 parts by weight with respect to 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer. Except that, a urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1.

In Example 1, OPPEA and 2-EHA were not added when preparing the photocurable composition, and the content of the urethane (meth)acrylate-based resin was adjusted to 25 parts by weight based on 100 parts by weight of the photocurable composition, and urethane (meth) Based on 100 parts by weight of the acrylate-based resin, except that the content of IBOA was adjusted to 220 parts by weight, the content of 2-HEA to 80 parts by weight, and the content of the photoinitiator was adjusted to 0.4 parts by weight, in the same manner as in Example 1, A burning composition and a substrate for a semiconductor process were prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 40,100 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,850 cP at 25° C. measured by a Brookfield viscometer (rotational speed of 10 rpm) on the No. 40 spindle.

Example 4

In Example 1 above, 2-EHA was added instead of IBOA when preparing the first mixture. In addition, based on 100 parts by weight of Nippollan 963, the content of TMDI was adjusted to 12.3 parts by weight, and the content of 2-HEMA was adjusted to 5.79 parts by weight with respect to 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer, except that A urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1.

In Example 1, OPPEA was not added when preparing the photocurable composition, and the content of the urethane (meth)acrylate-based resin was adjusted to 25 parts by weight based on 100 parts by weight of the photocurable composition, and the urethane (meth)acrylate-based resin Based on 100 parts by weight, the photocurable composition was carried out in the same manner as in Example 1, except that the content of 2-EHA was adjusted to 220 parts by weight, the content of 2-HEA was adjusted to 80 parts by weight, and the content of the photoinitiator was adjusted to 0.4 parts by weight. and a substrate for a semiconductor process was prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 42,300 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,910 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Example 5

In Example 1, based on 100 parts by weight of Nipollan 963, the content of TMDI was adjusted to 12.1 parts by weight, and the content of 2-HEMA was adjusted to 5.79 parts by weight based on 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer. Except that, a urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1.

In addition, 2-hydroxy-3-phenoxy propyl acrylate (PEG001, Hannong Chemical Co., Ltd.) was added during the preparation of the photocurable composition in Example 1, and urethane (meth)acryl based on 100 parts by weight of the photocurable composition The content of the rate-based resin is adjusted to 25 parts by weight, the content of IBOA is 132 parts by weight based on 100 parts by weight of the urethane (meth)acrylate-based resin, the content of 2-EHA is 20 parts by weight, and the content of OPPEA is 68 parts by weight. , A photocurable composition and a substrate for a semiconductor process were prepared in the same manner as in Example 1, except that the content of 2-HEA was adjusted to 40 parts by weight, the content of PEG001 was adjusted to 40 parts by weight, and the content of the photoinitiator was adjusted to 0.4 parts by weight. prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 43,650 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,780 cP at 25° C. measured with a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Example 6

In Example 1 above, 2-EHA was added instead of IBOA when preparing the first mixture. In addition, based on 100 parts by weight of Nippollan 963, the content of TMDI was adjusted to 12 parts by weight, and the content of 2-HEMA was adjusted to 5.81 parts by weight with respect to 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer, except that A urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1.

In addition, OPPEA and 2-HEA were not added during the preparation of the photocurable composition in Example 1, and the content of the urethane (meth)acrylate-based resin was adjusted to 22 parts by weight based on 100 parts by weight of the photocurable composition, ( In the same manner as in Example 1, except that the content of 2-EHA was adjusted to 355 parts by weight and the content of the photoinitiator to 0.45 parts by weight based on 100 parts by weight of the meth)acrylate-based resin, a photocurable composition and a semiconductor process The substrate was prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 47,500 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,840 cP at 25° C. measured with a Brookfield viscometer (rotational speed of 10 rpm) on spindle No. 40.

Comparative Example 1

In Example 1, isophorone diisocyanate (IPDI) was used instead of TMDI, the content of IPDI was adjusted to 12.8 parts by weight based on 100 parts by weight of Nippollan 963, and 100 parts by weight of polyalkylene carbonate-based urethane prepolymer With respect to parts, a urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1, except that the content of 2-HEMA was adjusted to 5.76 parts by weight.

In addition, the content of the urethane (meth)acrylate-based resin is adjusted to 22 parts by weight based on 100 parts by weight of the photocurable composition, and the content of IBOA is adjusted to 163 parts by weight, 2- based on 100 parts by weight of the urethane (meth)acrylate-based resin In the same manner as in Example 1, except that the content of EHA was adjusted to 23 parts by weight, the content of OPPEA was adjusted to 77 parts by weight, the content of 2-HEA was adjusted to 91 parts by weight, and the content of the photoinitiator was adjusted to 0.45 parts by weight, Compositions and substrates for semiconductor processing were prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 43,500 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,660 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Comparative Example 2

In Example 1, isophorone diisocyanate (IPDI) was used instead of TMDI, the content of IPDI was adjusted to 12.4 parts by weight based on 100 parts by weight of Nippollan 963, and 100 parts by weight of polyalkylene carbonate-based urethane prepolymer With respect to parts, a urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1, except that the content of 2-HEMA was adjusted to 5.78 parts by weight.

In Example 1, OPPEA and 2-EHA were not added when preparing the photocurable composition, and the content of the urethane (meth)acrylate-based resin was adjusted to 18 parts by weight based on 100 parts by weight of the photocurable composition, and urethane (meth) Based on 100 parts by weight of the acrylate-based resin, the photocurable type in the same manner as in Example 1, except that the content of IBOA was adjusted to 344 parts by weight, the content of 2-HEA to 111 parts by weight, and the content of the photoinitiator to 0.56 parts by weight. Compositions and substrates for semiconductor processing were prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 74,200 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,600 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Comparative Example 3

In Example 1, dicyclohexylmethane-4,4'-diisocyanate methylene-bis-(4-isocyanatocyclohexane) (H12MDI) was used instead of TMDI, and Nippollan 963 was used based on 100 parts by weight , except that the content of H12MDI was adjusted to 15 parts by weight, and the content of 2-HEMA was adjusted to 5.65 parts by weight based on 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer, urethane (meth ) An acrylate-based resin was prepared.

In addition, 2-hydroxy-3-phenoxy propyl acrylate (PEG001, Hannong Chemical Co., Ltd.) was added during the preparation of the photocurable composition in Example 1, and urethane (meth)acryl based on 100 parts by weight of the photocurable composition The content of the rate-based resin is adjusted to 20 parts by weight, the content of IBOA is 165 parts by weight based on 100 parts by weight of the urethane (meth)acrylate-based resin, the content of 2-EHA is 25 parts by weight, and the content of OPPEA is 85 parts by weight. , A photocurable composition and a substrate for a semiconductor process were prepared in the same manner as in Example 1, except that the content of 2-HEA was adjusted to 75 parts by weight, the content of PEG001 to 50 parts by weight, and the content of the photoinitiator was adjusted to 0.5 parts by weight. prepared.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 46,800 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,670 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Comparative Example 4

In Example 1, based on 100 parts by weight of Nippollan 963, the content of TMDI was adjusted to 14 parts by weight, and the content of 2-HEMA was adjusted to 5.7 parts by weight with respect to 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer. Except that, a urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1.

In addition, a photocurable composition and a substrate for a semiconductor process were prepared in the same manner as in Example 1.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 27,150 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,210 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Comparative Example 5

In Example 1, using N982R instead of Nippollan 963, adjusting the content of TMDI to 12.6 parts by weight based on 100 parts by weight of N982R, and 100 parts by weight of polyalkylene carbonate-based urethane prepolymer, 2-HEMA A urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1, except that the content was adjusted to 5.77 parts by weight.

In addition, a photocurable composition and a substrate for a semiconductor process were prepared in the same manner as in Example 1.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 40,100 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,840 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Comparative Example 6

In Example 1, using T5652 instead of Nippollan 963, adjusting the content of TMDI to 13.3 parts by weight based on 100 parts by weight of T5652, and 100 parts by weight of a polyalkylene carbonate-based urethane prepolymer, 2-HEMA A urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1, except that the content was adjusted to 5.74 parts by weight.

In addition, a photocurable composition and a substrate for a semiconductor process were prepared in the same manner as in Example 1.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 40,100 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,850 cP at 25° C. measured by a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

Comparative Example 7

In Example 1, using Capa2201A instead of Nippollan 963, adjusting the content of TMDI to 12.7 parts by weight based on 100 parts by weight of Capa2201A, and 100 parts by weight of polyalkylene carbonate-based urethane prepolymer, 2-HEMA A urethane (meth)acrylate-based resin was prepared in the same manner as in Example 1, except that the content was adjusted to 5.77 parts by weight.

In addition, a photocurable composition and a substrate for a semiconductor process were prepared in the same manner as in Example 1.

The weight average molecular weight of the prepared urethane (meth)acrylate-based resin was 45,600 g/mol. In addition, the prepared photocurable composition had a viscosity of 1,980 cP at 25° C. measured with a Brookfield viscometer (rotation speed of 10 rpm) on spindle No. 40.

(One) (2) (3) (4) (5) (6) IBOA OPPEA 2EHA 2HEA PEG001 Example 1 25 132 68 20 80 - 0.4 Example 2 19 205 89 26 105 - 0.5 Example 3 25 220 - - 80 - 0.4 Example 4 25 - - 220 80 - 0.4 Example 5 25 132 68 20 40 40 0.4 Example 6 22 - - 355 - - 0.45 Comparative Example 1 22 163 77 23 91 - 0.45 Comparative Example 2 18 344 - - 111 - 0.56 Comparative Example 3 20 165 85 25 75 50 0.5 Comparative Example 4 25 132 68 20 80 - 0.4 Comparative Example 5 25 132 68 20 80 - 0.4 Comparative Example 6 25 132 68 20 80 - 0.4 Comparative Example 7 25 132 68 20 80 - 0.4

In Table 1, “(1)” refers to a urethane (meth)acrylate-based resin, “(2)” refers to a cyclic alkyl group-containing (meth)acrylate-based monomer, and “(3)” refers to refers to an aromatic group-containing (meth)acrylate-based monomer, “(4)” refers to an alkyl group-containing (meth)acrylate-based monomer, and “(5)” refers to a polar functional group-containing (meth)acrylate-based monomer and "(6)" means a photoinitiator.

In addition, in Table 1, the content of (1) is based on 100 parts by weight of the photocurable composition, and the content of (2) to (6) is based on 100 parts by weight of the urethane (meth)acrylate-based resin.

* In Comparative Examples 5 to 7, a polyalkylene carbonate-based polyol including a carbonate repeating unit containing alkylene having 1 to 10 carbon atoms to which at least one side chain having 1 to 3 carbon atoms is bonded was not used.

Experimental example: high temperature knife cutting experiment

A high-temperature knife-cutting experiment was performed on the substrate for semiconductor processing prepared in Example 1 in the following manner.

Specifically, the substrate for the semiconductor process prepared in Example 1 was cut using a cutting device (manufactured by LG Chem) capable of controlling the temperature and cutting speed of the blade. At this time, the temperature of the blade was 170 ° C, the cutting speed was 300 mm/s, and the cutting angle was set to 90 °.

Thereafter, the cut surface of the cut semiconductor process substrate was observed, and when the size of the maximum foreign material was 70 μm or less, “OK” was evaluated, and when the size of the maximum foreign material was more than 70 μm, it was evaluated as “NG”.

High-temperature knife cutting experiments were also performed on the substrates for semiconductor processes prepared in Examples 2 to 6 and Comparative Examples 1 to 8, and the evaluation results are shown in Table 2 below.

Mw
(g/mol) Viscosity
(cP, 25°C) High Temperature Knife Cutting Results Example 1 47,800 1,910 OK Example 2 79,900 1980 OK Example 3 40,100 1,850 OK Example 4 42,300 1,910 OK Example 5 43,650 1,780 OK Example 6 47,500 1,840 OK Comparative Example 1 43,500 1,660 NG Comparative Example 2 74,200 1,600 NG Comparative Example 3 46,800 1,670 NG Comparative Example 4 27,150 1,210 NG Comparative Example 5 40,100 1,840 NG Comparative Example 6 40,100 1,850 NG Comparative Example 7 45,600 1980 NG

Referring to Tables 1 and 2, it was confirmed that the substrates for semiconductor processing prepared in Examples 1 to 6 of the present invention had excellent high-temperature knife cutting results. On the other hand, it was confirmed that all of the substrates for the semiconductor process prepared in Comparative Examples 1 to 7 were inferior in high temperature knife cutting results.

Therefore, it can be seen that the photocurable composition according to an exemplary embodiment of the present invention can implement a coating layer in which burr generation is effectively suppressed at a cutting blade with a high-temperature knife. Therefore, it can be seen that the substrate for semiconductor processing provided with the coating layer suppresses the generation of burrs at the cutting blade with a high-temperature knife, thereby effectively preventing damage and deformation of the wafer during wafer processing.

100: substrate for semiconductor process
10: base film
20: coating layer
30: hard coating layer

Claims (13)

a urethane (meth)acrylate-based resin that is a reaction product of a polyalkylene carbonate-based urethane prepolymer having an isocyanate terminal group and a reactive group-containing (meth)acrylate-based compound; and
At least one of an alkyl group-containing (meth)acrylate-based monomer, a cyclic alkyl group-containing (meth)acrylate-based monomer, an aromatic group-containing (meth)acrylate-based monomer, and a polar functional group-containing (meth)acrylate-based monomer (meth) acrylate-based monomer; including,
The polyalkylene carbonate-based urethane prepolymer is a reaction product of a polyalkylene carbonate-based polyol and an aliphatic acyclic diisocyanate-based compound,
The polyalkylene carbonate-based polyol is a photocurable composition comprising a carbonate repeating unit containing an alkylene having 1 to 10 carbon atoms to which at least one side chain having 1 to 3 carbon atoms is bonded.
The method according to claim 1,
The weight average molecular weight of the urethane (meth) acrylate-based resin is 40,000 g / mol or more of the photocurable composition.
The method according to claim 1,
The photocurable composition has a viscosity of 2,000 cP or less.
The method according to claim 1,
The aliphatic acyclic diisocyanate-based compound is a photocurable composition comprising a linear alkylene-containing diisocyanate compound having 1 to 10 carbon atoms.
The method according to claim 1,
The content of the aliphatic acyclic diisocyanate compound is 5 parts by weight or more and 13.5 parts by weight or less based on 100 parts by weight of the polyalkylene carbonate-based polyol.
The method according to claim 1,
The content of the reactive group-containing (meth)acrylate-based compound is 1 part by weight or more and 10 parts by weight or less, based on 100 parts by weight of the polyalkylene carbonate-based urethane prepolymer.
The method according to claim 1,
The content of the urethane (meth) acrylate-based resin is 15 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the photocurable composition.
The method according to claim 1,
The (meth) acrylate-based monomer includes the alkyl group-containing (meth) acrylate-based monomer,
The content of the alkyl group-containing (meth) acrylate-based monomer is based on 100 parts by weight of the urethane (meth) acrylate-based resin, 10 parts by weight or more and 400 parts by weight or less.
The method according to claim 1,
The (meth) acrylate-based monomer includes the cyclic alkyl group-containing (meth) acrylate-based monomer,
The content of the cyclic alkyl group-containing (meth) acrylate-based monomer is 100 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the urethane (meth) acrylate-based resin.
The method according to claim 1,
The (meth) acrylate-based monomer includes the aromatic group-containing (meth) acrylate-based monomer,
The content of the aromatic group-containing (meth) acrylate-based monomer is 50 parts by weight or more and 100 parts by weight or less, based on 100 parts by weight of the urethane (meth) acrylate-based resin.
The method according to claim 1,
The (meth) acrylate-based monomer includes the polar functional group-containing (meth) acrylate-based monomer,
The content of the polar functional group-containing (meth) acrylate-based monomer is based on 100 parts by weight of the urethane (meth) acrylate-based resin, 50 parts by weight or more and 110 parts by weight or less of the photocurable composition.
The method according to claim 1,
It further comprises a photoinitiator,
The content of the photoinitiator is based on 100 parts by weight of the urethane (meth) acrylate-based resin, 0.2 parts by weight or more and 60 parts by weight or less of the photocurable composition.
base film; and
A substrate for a semiconductor process comprising a; a coating layer comprising a cured product of the photocurable composition according to claim 1 .

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