KR20200143145A - Protected Organic-Inorganic hybrid Coating composition for dicing of Wafer and the Coating Material manufacturing thereof - Google Patents

Abstract

The present invention relates to an organic-inorganic composite protective coating agent for wafer processing, which prevents fundamentally prevents damage onto a wafer surface during processing including wafer cutting during a semiconductor manufacturing process by forming an organic-inorganic composite resin coating layer on the wafer surface, and is capable of manufacturing a protective coating agent which can increase stain resistance and adhesion.

Description

[Protected Organic-Inorganic hybrid Coating composition for dicing of Wafer and the Coating Material manufacturing thereof]

The present invention relates to a protective organic-inorganic composite coating composition for processing a wafer to make a semiconductor, and more particularly, to a protective organic-inorganic composite coating composition for wafer dicing that can be coated on the surface of a wafer to protect the surface of the wafer during the manufacturing process. It relates to a composite coating composition and a protective coating for wafer processing comprising the same.

In the semiconductor wafer processing process, the dicing process is also called sawing, and is a process of separating the wafer into individual chip units by being located between the wafer manufacturing process and the packaging process among the semiconductor production processes.

At this time, in order to protect the surface of the semiconductor wafer, a film for dicing a semiconductor wafer is adhered to the surface of the semiconductor wafer. This film for dicing a semiconductor wafer is attached to the backgrind surface to keep the cut chips during dicing and Then, it continues to play a role in moving the distributed chips to the bonding process. For this reason, contradicting performance, such as a holding force that does not cause chips to scatter during dicing and easy peelability during pick-up, is required at the same time, and many studies are being conducted in design. . Such a film for dicing a semiconductor wafer has been required not only to be easily peeled off, but also to not leave an adhesive on the wafer and to be free from contamination due to the miniaturization and thinning of the semiconductor.

Thus, conventionally, a technology related to a dicing/die-bonding film has been applied for patents in Korean Laid-Open Patent Publication Nos. 2004-34479 and 2004-103450, which have been applied for a patent as a technology developed to meet the above and physical properties. Considering the adhesive performance between the sealing/die bonding film and the semiconductor wafer, only the characteristics of the adhesive applied to the adhesive layer were considered.This method was useful because the processing time was short and the amount of debris was small when the size of the semiconductor chip was large. As the size decreases, the processing time increases and the amount of debris generated increases, so that it is impossible to remove the debris immediately, so that defects such as scratches and imprints are still not resolved by the remaining debris.

Accordingly, there is a need for a protective coating agent for wafer processing that can fundamentally block defects such as scratches, imprints, stains, whitening or corrosion that occur during processing including cutting processes by forming a coating layer on the wafer surface.

On the other hand, such a film for dicing a semiconductor wafer is peeled after the dicing process is completed, and conventionally, as a means for peeling it, it is known, for example, disclosed in Japanese Unexamined Patent Application Publication No. 2001-7179. That is, the double-sided adhesive layer is of an ultraviolet curable type whose adhesive strength is lowered by irradiation of ultraviolet rays. First, the adhesion is lowered in advance by irradiation with ultraviolet rays. Next, the semiconductor wafer is sandwiched between the upper and lower tables and heated in a vacuum-adsorbed state, and the double-sided adhesive layer is contracted and deformed to reduce the contact area between the double-sided adhesive layer and the semiconductor wafer, and the semiconductor wafer is floated. In addition, as the double-sided adhesive layer used herein, in addition to an ultraviolet curing type, a heat release property in which the adhesive strength decreases by foaming by heating is used.

However, if ultraviolet rays are irradiated on the circuit formation surface of the wafer, there is a fear of destroying the device (CCD or CMOS). As another means for peeling the support plate held by bonding to a semiconductor wafer via an adhesive layer, it is known to clean the peeling surface of the wafer using a cleaning liquid.

However, even after cleaning, there is a problem that the adhesive still remains on the peeling side of the wafer, resulting in a decrease in the quality or yield of the semiconductor device.

Moreover, in the case of the organic peeling composition, not only has a long cleaning time after peeling and a high environmental treatment cost, but also has a problem in terms of cost to be applied to the single wafer type method that is applied as the size of the wafer is largely cured.

Accordingly, there is a need for a release agent for wafer processing that can easily remove the adhesive layer remaining on the wafer surface and does not cause damage such as corrosion to the surface of the wafer.

Technology developed recently as a coating agent for wafer protection 10-1928831, 10-1860549 All of the protective coating agents are organic resins, and there is a possibility or application of a photosensitive resin, urethane type, and acrylic type.

On the other hand, acrylic and photosensitive resin coating materials lack some of the disadvantages of organic resins, such as adhesion and stain resistance. On the other hand, inorganic resin has excellent hardness and stain resistance, but has disadvantages of workability and brittle.

The invention was devised in consideration of the above points, and the organic-inorganic composite coating agent for wafer dicing with improved contamination resistance and improved contamination resistance by protecting the surface during processing of wafers during the semiconductor manufacturing process. There is a purpose to provide.

In addition, an object of the present invention is to provide a release agent for wafer processing capable of easily removing the protective dicing coating agent for wafer processing without damage or corrosion of the wafer surface.

This patent synthesizes organic-inorganic composite resins that have the merits of organic resins and inorganic resins to improve the yield by exceeding the limits of hardness and contamination, as well as secure a decrease in peeling by increasing the hardness, thereby improving the yield to protect the wafer. I want to apply it as a coating material.

In order to solve the above problems, it provides a composition of a coating agent for wafer processing comprising 5 to 65 parts by weight of an organic-inorganic composite resin, 30 to 90 parts by weight of a polar organic solvent or water, 0.0001 to 5 parts by weight of a surfactant and an additive. .

In a preferred embodiment of the present invention, the organic-inorganic composite resin may include a compound represented by Formula 6 below having a weight average molecular weight (Mw) of 100 to 30,000.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 6 to 9, R and R ₁ are each independently a hydrogen atom, a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, or a substituted or unsubstituted C5 -30 may be an aryl group, preferably, R and R1 are a hydrogen atom, an alkyl group having 4 or less carbon atoms, a cycloalkyl group having 5 to 24 carbon atoms, or an aryl group having 5 to 24 carbon atoms, and n is 0 to 30 Is a rational number within the range of, and m may be a rational number such that the weight average molecular weight (Mw) of the compound represented by Formulas 6 to 9 is 100 to 30,000.

Meanwhile, in a preferred embodiment of the present invention, a first process of coating the wafer surface with a compound represented by Chemical Formulas 6 to 9; A second step of placing the wafer in a pulling device; A third process of dicing the wafer; A fourth process of sorting and arranging only good products among the parts cut by the dicing process; A fifth process of peeling the coating composition from the selected good products; And a sixth process of inspecting good products from which the coating composition has been peeled off.

Here, in the first process, the process of coating the wafer surface with the compound represented by Formula 6 may be performed at 0 to 50° C. for 1 to 240 seconds.

According to the protective coating composition for wafer processing of the present invention and the organic-inorganic composite protective coating for wafer processing comprising the same, by forming a protective coating layer including an organic-inorganic composite resin on the surface of the wafer, it includes a cutting process of the wafer during the semiconductor manufacturing process. There is an effect of fundamentally preventing damage or contamination caused by foreign matters occurring on the wafer surface in the processing process.

This is a method of supplementing the existing contamination and hardness of organic resins with the characteristics of inorganic resins and supplementing the workability of inorganic resins with organic resins. Specifically, organic resins are resins such as urethane, acrylic, polyester, epoxy, and inorganic resins. It is composed of an organic-inorganic complex water dispersion polymer combined with inorganic binders such as phosphorus siloxane, titanium, and zirconium.

This is composed by synthesizing each organic resin and inorganic resin, respectively, and then additionally synthesizing the organic-inorganic composite resin. These organic-inorganic composite protective coatings have physical properties that are cured by heat and are not affected by heat or ultraviolet rays after curing. , Water resistance and hardness are included, so that surface damage due to debris can be prevented without being affected by water during the manufacturing process, as well as features that are easily removed by an alkaline solution after the manufacturing process is completed. Have.

In addition, according to the release agent for wafer processing for peeling off the organic-inorganic composite protective coating according to the present invention, the protective coating formed on the surface of the wafer is included in a separate release agent composition in which the protective coating agent is formed on the surface of the wafer, thereby processing the wafer during the semiconductor manufacturing process. There is an effect of being able to easily remove the organic-inorganic composite protective coating formed on the wafer surface in the process without damaging the surface of the wafer.

In addition, since the release agent for wafer dicing processing of the organic-inorganic composite protective coating according to the present invention has hydrophilicity and can be easily mixed with water, a problem such as corrosion of the material during the peeling process does not occur, and organic materials such as alcohol It has the effect of being able to wash only with water without using a solvent.

1 is a SEM EDS diagram of the coated surface of the present invention.
2 is a SEM EDS diagram of the organic-inorganic composite titanate of the present invention.
3 is a structure of an inorganic resin.
4 is a structure of an organic resin.
5 is a synthetic drawing of a urethane-based organic-inorganic composite resin among organic-inorganic composite resins.
6 is a hydrogen nuclear magnetic resonance spectrum of a urethane-based organic-inorganic composite resin.
7 is an infrared spectrum of a polyester-based organic-inorganic composite resin.

In order to explain the present invention in more detail, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein. In the drawings, parts not related to the description are omitted in order to clearly describe the present invention, and the same reference numerals are added to the same or similar components throughout the specification.

Throughout the present specification, “substituted” of “substituted or unsubstituted” refers to deuterium, cyano group, halogen group, hydroxy group, nitro group, C1-24 alkyl group, C1-24 halogenated alkyl group, C2-24 alkenyl group , C2-24 alkynyl group, C1-24 heteroalkyl group, C6-24 aryl group, C7-24 arylalkyl group, C2-24 heteroaryl group or C2-24 heteroarylalkyl group, C1-24 alkoxy Group, C1-24 alkylamino group, C1-24 arylamino group, C1-24 heteroarylamino group, C1-24 alkylsilyl group, C6-24 arylsilyl group, C6-24 aryloxy group It means substituted with one or more selected substituents.

Throughout this specification, specific examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like, but are not limited thereto.

Throughout this specification, specific examples of the “alkylene group” include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 3-methylpentylene group, heptylene group, octylene group, decylene group, etc. However, it is not limited thereto.

Throughout this specification, specific examples of “aryl group” include phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl Group, phenanthryl group, pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like, but are not limited thereto.

A first aspect of the present invention is, (A) 10 to 70 parts by weight of an organic-inorganic composite resin obtained by reacting any one of a polyurethane-based compound, an epoxy compound, a polyester-based compound, and an acrylic compound with an inorganic siloxane resin compound; And (B) 30 to 90 parts by weight of a solvent; It provides a protective coating composition for a dicing process containing.

In an embodiment, the organic-inorganic composite resin is based on 100 parts by weight of the total composition, 10 to 70 parts by weight, 10 to 60 parts by weight, 10 to 50 parts by weight, 10 to 40 parts by weight, 10 to 30 parts by weight, 10 to 20 parts by weight, 20 to 70 parts by weight, 20 to 60 parts by weight, 20 to 50 parts by weight, 20 to 40 parts by weight, 20 to 30 parts by weight, 30 to 70 parts by weight, 30 to 60 parts by weight, 30 to 50 parts by weight Parts, 30 to 40 parts by weight, 40 to 70 parts by weight, 40 to 60 parts by weight, 40 to 50 parts by weight, 50 to 70 parts by weight, 50 to 60 parts by weight, or 60 to 70 parts by weight.

In an embodiment, the solvent is 30 to 90 parts by weight, 30 to 80 parts by weight, 30 to 70 parts by weight, 30 to 60 parts by weight, 30 to 50 parts by weight, 30 to 40 parts by weight based on 100 parts by weight of the total composition. , 40 to 90 parts by weight, 40 to 80 parts by weight, 40 to 70 parts by weight, 40 to 60 parts by weight, 40 to 50 parts by weight, 50 to 90 parts by weight, 50 to 80 parts by weight, 50 to 70 parts by weight, 50 It may be to 60 parts by weight, 60 to 90 parts by weight, 60 to 80 parts by weight, 60 to 70 parts by weight, 70 to 90 parts by weight, 70 to 80 parts by weight, or 80 to 90 parts by weight.

In an embodiment, the protective coating composition for a dicing process may further include 0.0001 to 5 parts by weight of an additive. For example, the protective coating composition for the dicing process is additive 0.0001 to 5 parts by weight, 0.0001 to 4 parts by weight, 0.0001 to 3 parts by weight, 0.0001 to 2 parts by weight, 0.0001 to 1 part by weight, 0.0001 to 0.1 parts by weight, 0.0001 To 0.01 parts by weight, 0.0001 to 0.001 parts by weight, 0.001 to 5 parts by weight, 0.001 to 4 parts by weight, 0.001 to 3 parts by weight, 0.001 to 2 parts by weight, 0.001 to 1 parts by weight, 0.001 to 0.1 parts by weight, 0.001 to 0.01 Parts by weight, 0.01 to 5 parts by weight, 0.01 to 4 parts by weight, 0.01 to 3 parts by weight, 0.01 to 2 parts by weight, 0.01 to 1 parts by weight, 0.01 to 0.1 parts by weight, 0.1 to 5 parts by weight, 0.1 to 4 parts by weight , 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, 0.1 to 1 parts by weight, 1 to 5 parts by weight, 1 to 4 parts by weight, 1 to 3 parts by weight, 1 to 2 parts by weight, 2 to 5 parts by weight, 2 To 4 parts by weight, 2 to 3 parts by weight, 3 to 5 parts by weight, 3 to 4 parts by weight, or 4 to 5 parts by weight may be further included. The additive may include one or more of a surface control additive, a fluidity modifier, and an adhesion promoter, but is not limited thereto.

In an embodiment, the siloxane inorganic resin compound may include at least one of Si, Ti, Al, and Zr.

In an embodiment, the siloxane inorganic resin compound may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, M is Si, Ti, Al, or Zr, and R and R1 are each independently a hydrogen atom, a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C5-30 It is a cycloalkyl group, or a substituted or unsubstituted C5-30 aryl group.

In an embodiment, the weight average molecular weight (Mw) of the organic-inorganic composite resin may be 100 to 30,000. For example, the weight average molecular weight (Mw) of the organic-inorganic composite resin is 100 to 30,000, 100 to 25,000, 100 to 20,000, 100 to 10,000, 100 to 5,000, 100 to 1,000, 1,000 to 30,000, 1,000 to 25,000, 1,000 to 20,000, 1,000 to 15,000, 1,000 to 10,000, 1,000 to 5,000, 5,000 to 30,000, 5,000 to 25,000, 5,000 to 20,000, 5,000 to 15,000, 5,000 to 10,000, 10,000 to 30,000, 10,000 to 25,000, 15,000 to 20,000, 20,000 to 30,000, It may be 20,000 to 25,000, or 25,000 to 30,000, but is not limited thereto.

In an embodiment, the polyurethane-based compound may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R ₀ is a substituted or unsubstituted C1-10 alkylene group, a substituted or unsubstituted C5-30 arylene group, or a substituted or unsubstituted C5-30 cycloalkylene group, wherein R ₂ is a methyl, ethyl, or propyl group, R3 is a hydrogen, methyl, ethyl, propyl, butyl, or pentyl group, and A is triethylamine, dimethylaniline, or triphenylaniline.

In a preferred embodiment, R ₀ is

,

,

,

,

,

, 또는

일 수 있으나, 이에 제한되지 않는다. 여기에서, 상기 R은 C1-5의 알킬기일 수 있다.

,

,

,

,

,

, or

May be, but is not limited thereto. Here, R may be a C1-5 alkyl group.

In an embodiment, the epoxy compound may be a compound represented by Formula 3 below.

[Formula 3]

In Formula 3, m is a rational number in the range of 0 to 30, and n is a rational number in the range of 0.1 to 13.

In an embodiment, the epoxy compound may include at least one glycidyl group and at least one ethylene glycol group.

In an embodiment, the polyester-based compound may be a compound represented by Formula 4 below.

[Formula 4]

In Formula 4, m is a rational number of 1 to 60, and n is a rational number in the range of 0 to 60.

In a preferred embodiment, the polyester-based compound may be a polyvinyl ester.

In an embodiment, the acrylic compound may be a compound represented by the following formula (5).

[Formula 5]

In Formula 5, n is a free number within the range of 0 to 30.

In a preferred embodiment, the acrylic compound may be one or more of butyl acrylate, acrylonitrile, and butyl methacrylate.

A second aspect of the present invention provides an organic-inorganic protective coating for a dicing process comprising the protective coating composition for a dicing process according to the first aspect of the present invention.

A third aspect of the present invention is a first process of coating a wafer surface with a protective coating agent for a dicing process according to the second aspect of the present invention; A second step of placing the wafer in the pulling device; It provides a wafer dicing process including; and a third process of dicing the wafer.

Conventionally, as the size of the semiconductor chip becomes smaller, the processing time increases and the amount of debris generated increases, making it difficult to immediately remove the debris, and thus it is difficult to protect the wafer surface by the debris. Accordingly, in the present invention, by reacting an organic resin with an inorganic resin to synthesize an organic-inorganic composite resin and providing an organic-inorganic composite coating composition for wafer processing comprising a compound represented by the following formula (1) and a protective organic-inorganic composite coating for wafer processing comprising the same , Sought to solve the above problems. In the following process, a chemical bond is formed by bonding through a reaction of a functional group of an organic resin and an alkoxide or silanol of an inorganic resin, and an organic-inorganic composite material is used as a coating material.

[Formula 10]

[Formula 11]

The inorganic resin used in the above is synthesized by adding silane to each colloidal sol, and includes silica, alumina, titania, and zirconia sol, and is synthesized by the following reaction process.

[Formula 12]

Here, M is one or more of Si, Ti, Al, or Zr, n is a rational number of 0 to 30, and m is independently a weight average molecular weight (Mw) of the compound represented by Formulas 6 to 9 It is a rational number that satisfies ~30,000.

The coating composition according to the present invention may include 10 to 70% by weight of the total weight of the coating composition of the organic-inorganic composite resin represented by Chemical Formulas 6 to 9. Preferably it may contain 20 to 50% by weight, more preferably may contain 25 to 45% by weight. At this time, if the content of the organic-inorganic composite resin is less than 10% by weight, there may be a problem in that the coating is not properly performed, and if it exceeds 70% by weight, there may be a problem that the coating becomes uneven, so it is recommended to use within the above range.

The polar organic solvent, which is one of the coating composition of the present invention, serves to dissolve the organic-inorganic composite resin, and may include 25 to 80% by weight of the total weight of the coating composition. Preferably, it may contain 50 to 70% by weight, more preferably 55 to 65% by weight. At this time, if the content of the polar organic solvent is less than 25% by weight, there may be a problem that the organic-inorganic resin is precipitated, and if it exceeds 80% by weight, there may be a problem that the coating is not properly performed, so it is recommended to use within the above range.

In addition, the polar organic solvent may be used alone or in combination of two or more selected from alcohols, ketones and glycol ethers, preferably one selected from alcohols and ketones, or a mixture of two or more. , More preferably, it is good to use alcohols.

One of the coating composition of the present invention, the additive for surface control, plays a role of imparting slip properties of the surface after coating, and may contain 0.0001 to 1% by weight of the total weight of the coating composition, and preferably 0.01 to 1% by weight. Can include.

At this time, if the content of the additive for surface control is less than 0.0001% by weight, there may be a problem of adhesion of foreign substances due to insufficient slip property, and if it exceeds 1% by weight, there may be a problem that the adhesion of the coating decreases. It is good. Preferably, the additive for surface control may be a silicone type, and specifically, PROTEX International's MODAREZ K-SE 305 (silicone), MODAREZ K-SL 106 (silicone), MODAREZ K-SL 107 (silicone) or BYK's BYK- 331, BYK-333 (silicon system), BYK-348 (silicon system), and BYK-3455 (silicon system) can be used.

As one of the coating composition of the present invention, the flow modifier serves to adjust the viscosity of the coating solution, and may contain 0.0001 to 1% by weight of the total weight of the coating composition, and preferably 0.01 to 1% by weight. I can. At this time, if the content of the fluidity modifier is less than 0.0001% by weight, the viscosity may be low and the coating thickness may be thin, and if it exceeds 1% by weight, the viscosity may be high and there may be a problem of uneven coating, so it is recommended to use it within the above range. good. In addition, the fluidity modifier may be PROX A 300, PROX AM 162 S, SYNTHRO THIX 608 of PROTEX International, or BYK-405, BYK-420, or BYK-7420 ES of BYK.

The adhesion promoter, which is one of the coating compositions of the present invention, serves to improve the adhesion of the coating, and may include 0.0001 to 1% by weight of the total weight of the coating composition, and preferably 0.01 to 1% by weight. . At this time, if the content of the adhesion promoter is less than 0.0001% by weight, there may be a problem that the adhesion of the coating is deteriorated, and if it exceeds 1% by weight, there may be a problem that the slip property of the coating is poor, so it is recommended to use within the above range. In addition, as the adhesion promoter, BYK-4509 and BYK-4500 of BYK may be used.

Preferably, it may include a method comprising the organic-inorganic composite coating composition for wafer processing.

In addition, the present invention is capable of removing the coating for wafer processing with the previously published release agent of 10- 1928830 including the release agent composition for wafer processing to remove the coating agent.

Here, the release agent may be effectively applied to remove the coating agent, the absolute viscosity of the release agent is 80 to 120 cps, the effective alkalinity is 20 to 35, and the pH may be 8 to 14. Preferably, the absolute viscosity of the peeling agent is 90 to 110 cps, the effective alkalinity is 25 to 30, and the pH may be 9 to 13, more preferably the absolute viscosity of the peeling agent is 95 to 105 cps, the effective alkalinity is 27 And the pH may be 10 to 12. At this time, if the absolute viscosity is less than 80 or more than 120, there may be a problem that the peeling is not properly performed, and if the effective alkalinity is less than 20, a problem of lowering the peeling performance may occur, and if it is more than 35 There may be problems causing corrosion. If the pH is less than 8, a problem of lengthening the peeling time may occur, and if the pH is more than 14, the solution becomes a strong alkaline solution and there may be a problem in wastewater treatment.

The present invention includes a first step of forming a coating layer by coating the wafer surface using a coating agent containing a compound represented by Chemical Formulas 6 to 9; A second step of placing the wafer in a pulling device; A third process of dicing the wafer; A fourth process of sorting and arranging only good products among the parts cut by the dicing process; A fifth step of peeling the coating layer from the selected good products using the wafer processing release agent; And a sixth step of inspecting the good products from which the coating layer has been peeled off.

Here, the fifth process may be performed at a temperature of 10°C to 50°C for 1 to 10 minutes, and preferably at a temperature of 20°C to 40°C for 1 to 5 minutes.

The fifth process may include a method of removing the wafer on which the coating layer is formed by immersing it in a container into which the release agent is injected.

Hereinafter, the present invention will be described in more detail through the following examples. At this time, the following examples are provided to aid understanding of the present invention, and do not limit the scope of the present invention.

[Examples 1 to 4] Preparation of inorganic resin

Colloidal silica, zirconium, alumina, and titanium were prepared as follows and added to a four-neck reactor. Thereafter, an appropriate pH and reaction catalyst were added, silane was added at room temperature, and reacted at about room temperature to 90° C. for an additional 3 hours to obtain an inorganic resin.

division Example 1 Example 2 Example 3 Example 4 Colloidal sol/ dosage (g) SILICA/100g ALUMINA/ 100g ZIRCONIA/ 100g TITANIA/ 100g Silane type and amount added (g) MTMS / 75g TEOS / 50g MTES: VINYL TRIMETHOXY SILANE=70:30 / 120g PHNEYLTRIMETHOXYSILANE / 200g Reaction solvent (g) IPA /200 ETOH / 300 ACTYL ACETONE:IPA=50:50 / 200 n-BUTANOL / 150 Bin temperature/time RT/4hr 80 ℃/ 6hr 80 ℃/ 6hr 90 ℃/ 4hr transparency Transparency hazy Transparency Transparency Pencil hardness
(180℃, curing for 30 minutes) 2~3H 2H 4H 4H Wafer adhesion 5B 4B 4B 4B Solution stability ⊙ ○ △ ⊙ Peelability Some residue BAD Some residue GOOD

⊙: Very good, ○: Excellent, △: Average

[Examples 5 to 8] Preparation of organic resin

<Example 5. Introduction and preparation of polyethylene glycol of epoxy>

In a 500 ml reactor, 100 g of polyethylene glycol (molecular weight 400 g/mol) was added to 350 g of bisphenol epoxy type (EEW=180) epoxy, and 1 g of caustic soda was added to react at 90° C. for 3 hours. I got an epoxy.

<Example 6. Preparation of urethane prepolymer>

1 mol of polycaprolactone diol was added to a 1000 ml reactor, heated to 80° C. to dissolve, and 2.8 mol of IPDI was added under a nitrogen atmosphere to react for 1 hour. 0.8 mol of dimehtylpropanoic acid and 0.5 mol of N-aminopropyltrimethoxy silane were diluted with 300 ml of n-methylpyrrolidone and added, followed by an additional reaction for 3 hours. This obtained a prepolymer in which the terminal group was substituted with NCO.

<Example 6-1. Preparation of urethane prepolymer>

It is prepared by replacing polycaprolactone diol with polycarbonatediol.

<Example 6-2. Preparation of urethane prepolymer>

It is prepared by replacing polycaprolactone diol with polytetramethylene etherdiol.

<Example 7. Preparation of polyester polymer>

After installing a dienstock device in a 500 ml flask, 136 g of pentaerythritol and 60 g of adipic acid were added, followed by adding 0.2 g of p-toluenesulfonic acid, followed by reaction at 180° C. for 4 hours. Thereafter, the catalyst was removed with alkali, and then moisture was removed by vacuum to obtain a polymer.

<Example 8. Synthesis of siloxane-introduced acrylic polymer>

A reflux cooler and a nitrogen injection device were prepared, and 3 g of inorganic resin 1 and 30 g of polyvinyl alcohol were reacted at 80° C. for 4 hours in a 1000 ml reactor, followed by mixing and stirring with 100 ml of distilled water. Monomer butyl acrylate 60 g, acrylonitrile 30 g, butyl methacrylate 15 g, polyvinyl alcohol 3 g, and initiator sodium lauryl sulfate 0.9 g were mixed with 20 g of distilled water, and the reaction temperature was maintained at 70° C. and 200 rpm, followed by dropping for 4 hours. . After the reaction for 2 hours after dropping, 1 g of aqueous ammonia was injected for 1 hour in order to increase the viscosity.

<Example 9: Synthesis of polyvinyl ester into which siloxane>

15 g of the inorganic resin synthesized in Example 1 was heated to 50 g of polyvinyl alcohol and reacted for 3 hours at 80°C, and then to 500 g of Di water, 300 g of vinyl acetate monomer, 50 g of butyl acetate, and 3 g of potassium persulfate were added to react for 5 hours. Was synthesized.

<Examples 10-14: Synthesis of organic-inorganic composite resin>

Organic resin and inorganic resin were added and reacted as follows to obtain an organic-inorganic composite resin.

division Example 10 Example 11 Example 12 Example 13 Example 14 Comparative example
10-1928831/ 10-1860549 Organic resin/ added amount (g) Example 5/ 150g Example 6/ 150g Example 7 / 150g Example 8/ 150g Example 9/150g Inorganic resin/ added amount (g) Example 2/30g Example 1/20g Example 3/100g Example 4/10g (secondary reaction) Example 1/ 15g (secondary reaction) Catalyst (g) DBTDL 2g Acetic acid /1G Formic acid/0.5g Citric acid: 2g 1 g formic acid Reaction temperature after addition
(℃)/hour 80/4 hours 110/3 hours 70/5 hours 80/2 hours 80/4 hours After reaction
fair 2 hours of water dispersion in 50 g of DI water Add 3g of triethylamine and disperse in 100g of di water 2 hours of water dispersion in 150 g of DI water 2 hours of water dispersion in 100 g of DI water 2 hours of water dispersion in 100 g of DI water Attach
Enhancer trisilanolisobutylPOSS 1g 0.5 g octaphenylposs surface
additive 0.5g 1g Fouling resistance ⊙ ⊙ ⊙ ○ ○ X~△ Pencil hardness 2~3H 2~3H 4H 2~3H 2~3H 1~2H Adherence 3B 5B 4B 5B 4B 3B Peelability ⊙ ⊙ ○ ○ ○ ○ Coating properties ○ ○ ○ △ ○ ○

Curing conditions: 150℃, 20 minutes, spicoating: 500rpm, 20 sec,

Peelability test: Peeling using the peeling agent indicated in 10- 1928830

(Including tetraalkyl ammonium hydroxide and hydrophilic solvent-based release agent).

In the above, the organic resin is also possible to Examples 6, 6-1, 6-2, and 6-3, and exhibits similar performance.

As a result of applying the coating agent according to the present invention, it can be confirmed that the yield improvement and contamination prevention function of the semiconductor DICING process have excellent stain resistance and hardness, adhesion performance, peelability, and coating properties compared to the existing organic resin.

Claims (10)

(A) 10 to 70 parts by weight of an organic-inorganic composite resin obtained by reacting any one of a polyurethane compound, an epoxy compound, a polyester compound, and an acrylic compound with a siloxane inorganic resin compound; And
(B) 30 to 90 parts by weight of a solvent;
Containing, a protective coating composition for a dicing process. The method of claim 1,
The siloxane inorganic resin compound contains at least one of Si, Ti, Al, and Zr, a protective coating composition for a dicing process. The method of claim 1,
The siloxane inorganic resin compound is a compound represented by the following formula (1), a protective coating composition for a dicing process.
[Formula 1]

In Formula 1, M is Si, Ti, Al, or Zr, and R and R1 are each independently a hydrogen atom, a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C5-30 It is a cycloalkyl group, or a substituted or unsubstituted C5-30 aryl group. The method of claim 1,
The organic-inorganic composite resin has a weight average molecular weight (Mw) of 100 to 30,000, a protective coating composition for a dicing process. The method of claim 1,
The polyurethane-based compound is a compound represented by the following Formula 2, a protective coating composition for a dicing process.
[Formula 2]

In Formula 2, R ₀ is a substituted or unsubstituted C1-10 alkylene group, a substituted or unsubstituted C5-30 arylene group, or a substituted or unsubstituted C5-30 cycloalkylene group, wherein R ₂ is a methyl, ethyl, or propyl group, R ₃ is hydrogen, methyl, ethyl, propyl, butyl, or pentyl group, A is triethylamine, dimethylaniline, or triphenylaniline, and n is It is a rational number in the range of 1 to 30. The method of claim 1,
The epoxy compound is a compound represented by the following Chemical Formula 3, a protective coating composition for a dicing process.
[Formula 3]

In Formula 3, m is a rational number within the range of 0.1 to 13, and n is a rational number within the range of 0 to 30. The method of claim 1,
The polyester-based compound is a compound represented by the following Chemical Formula 4, a protective coating composition for a dicing process.
[Formula 4]

In Formula 4, m is a rational number of 1 to 60, and n is a rational number in the range of 0 to 60. The method of claim 1,
The acrylic compound is a compound represented by the following Chemical Formula 5, a protective coating composition for a dicing process.
[Formula 5]

In Formula 5, n is a free number within the range of 0 to 30. An organic-inorganic protective coating agent for a dicing process, comprising the protective coating composition for a dicing process according to any one of claims 1 to 8. A first step of coating the wafer surface with the protective coating agent for a dicing process according to claim 9;
A second step of placing the wafer in a pulling device; And
A third process of dicing the wafer;
Containing, a wafer dicing process.

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