KR101764167B1 - Coating Composition For Protecting Wafers In Laser Scribing Process - Google Patents

Abstract

The present invention provides a coating composition for protecting wafers, wherein the coating composition comprises with respect to 100 parts by weight of a high water-soluble polymer resin: 5-50 parts by weight of a polyurethane, a vinyl pyrrolidone/methacrylamide/vinyl imidazole copolymer, a vinyl pyrrolidone/vinyl alcohol copolymer, poly(vinyl acetate-co-crotonic acid), an aminoethylpropanediol-acrylate copolymer, or a mixture thereof; 1-10 parts by weight of a surfactant; 5-30 parts by weight of a hydrolysable silane compound; 10-30 parts by weight of a water-dispersible polyurethane dispersant; 3-10 parts by weight of nanoceramic particles; 3-10 parts by weight of a binder; and 50-150 parts by weight of a solvent. The coating composition for protecting wafers according to the present invention easily adheres to the surface of a wafer, and at the same time, improves adhesion, thereby protecting the wafer from being damaged upon laser scribing, and improves washability.

Description

Technical Field [0001] The present invention relates to a coating composition for protecting wafers in a laser scribing process,

The present invention relates to a coating composition for protecting wafers, and more particularly, to a coating composition for protecting wafers, which protects wafers during wafer scribing and improves cleanability during laser scribing for manufacturing semiconductors.

At present, the gap between streets becomes narrower due to integration and thickening of semiconductor devices, and is becoming more integrated.

Generally, the dicing process using a blade has excellent properties in terms of productivity and versatility, but problems such as damage due to blades due to large-scale curing and integration and difficulties in production itself occur.

In order to solve such a problem, a dicing process using a laser has been developed.

However, the laser dicing process has a problem in that it is subject to many restrictions in use due to contamination due to self heat generated during dicing, fume and / or debris.

In order to overcome the above-mentioned problems, Korean Patent Application No. 10-2009-0095592 discloses a poly (2-ethyl-2-oxazoline) and a water- (2-ethyl-2-oxazoline), it is difficult to prepare a composition due to the properties of being opaque at a certain temperature or above and low water solubility There is a problem that it is difficult.

Korean Patent Application No. 10-2015-0013315 discloses a composition using cross-linking of glutaraldehyde, which is applied to PVA (polyvinylalcohol), because glutaraldehyde alone has a characteristic It is difficult to say that it has been modified.

In Korean Patent Application No. 10-2005-0107577, a protective film is formed by using a laser light absorbent for a water-soluble resin. However, there is a problem that it is difficult to protect the wafer only by these constitutions.

Particularly, most of the above-mentioned conventional technologies use dispersing agents, crosslinking agents or surfactants dispersed in water-soluble polymers. However, when one or two water-soluble polymers are mixed, the function is somewhat weakened, So that the protective film is lifted up and foreign substances are deposited between the gaps. As a result, the cleaning property is reduced.

In order to overcome such a problem, adhesion and adhesion between the wafer surface and a coating film (protective film) for protecting the wafer surface are very important.

SUMMARY OF THE INVENTION The present invention has been made in order to overcome the above-described problems, and it is an object of the present invention to provide a coating agent composition which can easily adhere to a wafer surface and improve adhesion, prevent wafer from being damaged during laser scribing, .

The present invention

Based on 100 parts by weight of the water-soluble polymer resin,

Polyvinyl pyrrolidone / vinyl alcohol copolymer, poly (vinyl acetate-CO-crotonic acid), aminoethyl propanediol-acrylate copolymer, polyvinyl pyrrolidone / methacrylamide / vinyl imidazole copolymer, 5 to 50 parts by weight of a mixture thereof;

1 to 10 parts by weight of a surfactant;

5 to 30 parts by weight of a hydrolyzed silane compound;

10 to 30 parts by weight of a water-dispersed polyurethane dispersant;

3 to 10 parts by weight of nano-ceramic particles;

3 to 10 parts by weight of a binder; And

And 50 to 150 parts by weight of a solvent.

The coating composition for wafer protection according to the present invention has an effect of easily bonding to the surface of the wafer and improving the adhesiveness, thereby preventing the wafer from being damaged during laser scribing and improving the cleaning property.

Fig. 1 shows the result of measurement of the wafer surface of Example 1 according to the present invention.
2 shows the results of measurement of the wafer surface of Example 2 according to the present invention.
3 shows the results of measurement of the wafer surface of Example 3 according to the present invention.
4 shows the results of measurement of the wafer surface of Comparative Example 1 according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a water-soluble polymeric resin composition comprising, based on 100 parts by weight of a water-soluble polymer resin, at least one member selected from the group consisting of polyurethane, vinylpyrrolidone / methacrylamide / vinylimidazole copolymer, vinylpyrrolidone / vinyl alcohol copolymer, Acid), aminoethyl propanediol-acrylate copolymer or mixtures thereof 5 to 50 parts by weight; 1 to 10 parts by weight of a surfactant; 5 to 30 parts by weight of a hydrolyzed silane compound; 10 to 30 parts by weight of a water-dispersed polyurethane dispersant; 3 to 10 parts by weight of nano-ceramic particles; 3 to 10 parts by weight of a binder; And 50 to 150 parts by weight of a solvent.

The coating composition for protecting a wafer according to the present invention can prevent a wafer from being damaged during laser scribing and improve cleaning property by forming a coating film on a surface of a target to be coated (for example, a coating layer), for example, And is not particularly limited as long as it is a conventional coating composition in the art having such a purpose.

The water-soluble polymer resin according to the present invention is included in the coating composition for protecting wafers to improve the degree of adhesion, and any water-soluble polymer resin in the art having such a purpose may be used.

Preferred water soluble polymer resins include polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, polyacrylic acid, or mixtures thereof.

At this time, the water-soluble polymer resin can control the basic physical properties of the coating composition, the receiving planet and the surface adhesion by controlling the content ratio of the water-soluble polymer resin according to the degree of saponification and the molecular weight.

On the other hand, polyvinyl alcohol and polyvinylpyrrolidone in the water-soluble polymer resin have good solubility in water and have an excellent adhesion to a wafer to be coated.

The polyvinyl alcohol has a degree of saponification of 86 to 90% and is easy to use and applicable. Polyvinylpyrrolidone has a K-value of 13 to 130 and an average molecular weight of 6,000 to 2,000,000 Da. ≪ / RTI >

In particular, the water-soluble polymer resin according to the present invention differs in water solubility and water-dispersibility depending on saponification degree and molecular weight, and storage stability according to changes over time, so that the user appropriately selects and uses I recommend you.

The content of the components other than the water-soluble polymer resin of the coating composition according to the present invention, specifically the coating composition for protecting a wafer, is based on 100 parts by weight of the water-soluble polymer resin.

Vinyl pyrrolidone / vinyl imidazole copolymers, vinyl pyrrolidone / vinyl alcohol copolymers, poly (vinyl acetate-CO-crotonic acid), aminoethyl propanediol- Acrylate copolymer or a mixture thereof is used for improving the adhesion and cleaning property of the wafer protective coating composition and providing thermal stability. The amount of the coating agent used is 5 to 50 parts by weight based on 100 parts by weight of the water-soluble polymer resin good.

In this case, the above-mentioned copolymers such as polyurethane, vinylpyrrolidone / methacrylamide / vinylimidazole copolymer, vinylpyrrolidone / vinyl alcohol copolymer, poly (vinyl acetate-CO-crotonic acid) Aminoethyl propanediol-acrylate copolymers, or mixtures thereof, when used with water-soluble polymeric resins, further increases physical properties, such as adhesiveness.

On the other hand, when a polymer resin is used together with another polymer resin, the polymer resin may lose some of its inherent properties and exhibit new properties. However, in the case of the coating composition according to the present invention, , For example, at a temperature of about 80 캜 or more, the surface adhesiveness remarkably increases.

Thus, the water-soluble polymer resin and the copolymer mixture according to the present invention can change the adhesion and the strength on the coating surface depending on the mixing ratio and the polymerization time.

The surfactant according to the present invention is contained in a coating composition, specifically a wafer protective coating composition to provide cleansing and smoothness. Any conventional surfactant having such a purpose may be used, It is preferable to use polyethylene glycol, polyoxyalkylene glycol, polyethoxypropoxyalkyl glycol, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl ethers, polypropylene ethylene propylene copolymers, or a mixture thereof, It is recommended that the amount thereof is 1 to 10 parts by weight based on 100 parts by weight of the water-soluble polymer resin.

Particularly, besides the surfactant according to the present invention, anionic or cationic surfactants can be used. However, most of the anionic surfactants are used because of their cationic nature due to sulfates or other salts and cationic surfactants. It is not recommended to use it, as it is likely to corrode.

The hydrolyzed silane compound according to the present invention not only improves crack resistance, chemical resistance and the like, improves thermal stability and mechanical properties, but also improves thermal stability and mechanical properties of the water-dispersed polyurethane dispersant described later Any conventional hydrolyzed silane compound having such a purpose may be used, but it is recommended to use alkoxysilane, silane oxide or a mixture thereof.

The amount of the preferred hydrolyzed silane compound to be used is not particularly limited, but is preferably 5 to 30 parts by weight based on 100 parts by weight of the water-soluble polymer resin.

The water-dispersed polyurethane dispersant according to the present invention is contained in a coating composition for a wafer protective coating to improve environmental friendliness and adhesion (G / L, GI, EGL etc.), scratch resistance, water resistance, cold resistance, corrosion resistance and / The water-dispersible polyurethane dispersant may be any conventional water-dispersible polyurethane dispersing agent having such a purpose. The amount of the water-dispersible polyurethane dispersant to be used may be changed according to the user's choice. Preferably, 100 parts by weight of the water- 10 to 30 parts by weight.

As a specific embodiment, the water-dispersed polyurethane dispersant according to the present invention may be a prepolymer resin, IPDI (isophorone diisocyante), MDI (methyl diisocyanate), polyol (polytetramethyleneglycol, polyhexamethylene adipate). A prepolymer resin having an NCO-terminal group is prepared by using DMPA (dimethylolpropionic acid), DMS (dimethylol sulfate) or a mixture thereof as a starting material, and then a catalyst such as DBTL or DBTDL (dibutyltin dilaurate) TEA (triethylamine) and chain extender EDA (ethyl diamine).

The nanoceramic particles according to the present invention float on the surface of the coating composition for wafer protection to form a dense and hard surface, thereby preventing the permeation of water vapor and other gases and liquids, as well as preventing moisture, durability, Impact resistance and chemical resistance are improved.

The amount of the nanoceramic particles used is preferably 3 to 10 parts by weight based on 100 parts by weight of the water-soluble polymer resin.

Preferred nanoceramic particles include silicon carbide, alumina, silica, zirconia-silica, ZnO, TiO ₂ and / or CaCO ₃ .

It is preferable that the average particle size of the ceramic particles is in the range of nanometers. Specifically, the average particle size of the silicon carbide is 300 to 500 nm, the average particle size of the alumina is 500 to 1000 nm, the average particle size of the silica is 700 to 1500 nm, -The average particle size of silica is 500-1000 nm, the average particle size of ZnO is 500-1000 nm, the average particle size of TiO ₂ is 100-300 nm, and the average particle size of CaCO ₃ is 500-1000 nm.

Among them, silicon carbide does not exist as natural minerals, so it is synthesized artificially, has excellent chemical stability and corrosion resistance at high temperature, and has high hardness.

The binder according to the present invention allows the coating composition to be easily applied to a surface to be coated, and any binder common in the art to be used for such a purpose can be used.

The binder to be applied may be a thermoplastic resin, a thermosetting resin, a photocurable resin, a silane compound, a titanium compound, a polymer copolymer, a self-assembled resin or a mixture of at least one selected from the foregoing. More specifically, a melamine resin, , An unsaturated polyester resin, a phenol resin, an epoxy resin, a silicone resin, or a mixture of at least one selected from these may be used, and the amount thereof to be used is not particularly limited, but it is preferably 3 to 10 parts by weight based on 100 parts by weight of the polymer resin good.

The solvent according to the present invention is not particularly limited as long as it is a solvent commonly used in the art, but it is preferable to use alcohol, propylene glycol monomethyl ether, ethyl lactate or a mixture thereof, And 50 to 150 parts by weight based on 100 parts by weight.

In a particular embodiment, the coating composition according to the invention, in particular the wafer protective coating composition, further comprises 0.5 to 5 parts by weight of a surface smoothing agent based on 100 parts by weight of the water-soluble polymer resin in order to improve self-leveling .

The surface smoothing agent may be one or more selected from the group consisting of modified starch ether, polyoxide, urethane and polycarboxylic acid, but is not limited thereto. Can be used.

In another specific embodiment, the coating composition for protecting a wafer according to the present invention may further contain 1 to 20 parts by weight, based on 100 parts by weight of the water-soluble polymer resin, of a thickener for adjusting the viscosity to facilitate the use of the coating composition.

As a preferred thickening agent, it is recommended to use hydroxyethyl cellulose, a hydrophobic urethane modifier thickener, or a mixture thereof.

Here, the hydroxyethyl cellulose used as the thickener may have water retention property.

In another specific embodiment, the coating composition for protecting a wafer according to the present invention may further comprise 5 to 30 parts by weight of a plasticizer based on 100 parts by weight of the water-soluble polymer resin in order to smoothly perform a mixture between the components.

Preferred plasticizers are selected from the group consisting of terephthalic acid metal salts, stearic acid metal salts, petroleum resins, low molecular weight polyethylenes and low molecular weight polyamides.

In another specific embodiment, the coating composition for protecting a wafer according to the present invention may further include 0.5 to 5 parts by weight of an antifoaming agent based on 100 parts by weight of the water-soluble polymer resin in order to reduce an increase in the amount of air due to the generation of entrained air.

Preferred defoaming agents include mineral oil defoaming agents such as kerosene, paraffin, mineral oil and ethanol synthetic oil, retention defoaming agents such as animal and vegetable oils, sesame oil, castor oil and their alkylene oxide adducts, oleic acid, stearic acid and their alkylene oxides Fatty acid ester defoaming agents such as glycerin monolysinolate, alkenyl succinic acid liquid, sorbitol monolaurate, sorbitol trioleate, and natural wax, polyoxyalkylene, (poly) oxyalkyl ether Oxyalkylene antifoaming agents such as (poly) oxyalkylene alkylphosphoric acid esters, (poly) oxyalkylene alkylamines and (poly) oxyalkylene amides, octyl alcohol, hexadecyl alcohol, acetylene alcohol, Alcohol-based defoaming agents such as glycols, amide-based defoaming agents such as acrylate polyamines, tributyl phosphate, Octyl phosphoric acid ester base defoaming agents, such as phosphate, aluminum stearate, calcium oleate (polyorganosiloxanes such as dimethyl polysiloxane), metal soap-based defoaming agent, dimethyl silicone oil, silicone, pay seut, silicone emulsions, organic modified polysiloxanes such as. And silicone-based antifoaming agents such as fluorosilicone oil, etc., but is not limited thereto.

In another specific embodiment, the coating composition for protecting a wafer according to the present invention is characterized in that the coating composition for protecting a wafer has a high adhesion, a water resistance, a water permeability, an oxygen permeability, an ion permeability, an electrical insulating property, a chemical resistance, ) And the like, 10 to 40 parts by weight of the acrylic emulsion resin may be further added based on 100 parts by weight of the water-soluble polymer resin.

Preferred acrylic emulsion resins include monomers such as 2-ethylhexyl acrylate, 2-hydroethylmethacrylate, AN, acrylonitrile, butyl acrylate, methacrylic acid, methylmethacrylate ), SM (styrene monomer), diacetone acrylamide, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or a mixture thereof It is good to do.

In another specific embodiment, the coating composition for protecting a wafer according to the present invention may further comprise an anti-peeling agent to prevent the coating layer from being easily peeled off from the object surface to be formed.

As the preferable peeling inhibitor, it is preferable to use a polyphosphoric acid type, an amine type, or a phosphoric acid ester type peeling inhibitor.

Specifically, the anti-peeling agent is a liquid phase anti-peeling agent having a specific gravity of 1.0 or more and a viscosity at 60 DEG C of 110 cPs; The acid value is 10 mgKOH / g or less, and the total amine value is 140 to 400 mg HCl / g.

The amount of the anti-peeling agent is preferably 10 to 30 parts by weight based on 100 parts by weight of the water-soluble polymer resin.

In another specific embodiment, the coating composition for protecting a wafer according to the present invention may further comprise 2 to 8 parts by weight of tetraethylenepentamine (TEPA) based on 100 parts by weight of a water-soluble polymer resin, wherein the tetraethylenepentamine is a polyamine And has a role of controlling the curing speed and viscosity of the protective coating composition. When the amount is less than 2 parts by weight, the effect is insignificant. When the amount is more than 8 parts by weight, the amount is excessive and is not economical.

In another specific embodiment, the protective coating composition according to the present invention may further comprise octyltriethoxysilane to improve adhesion.

The octyltriethoxysilane may be used in the form of a monomer. The molecular weight of the monomer is not particularly limited, but is preferably 150 to 450 Da, and the amount of the octyltriethoxysilane used is 1 to 10 parts by weight based on 100 parts by weight of the polymer resin .

In another specific embodiment, the protective coating composition according to the present invention further comprises an amino-functional siloxane to effectively cure at room temperature and to provide improved properties such as heat resistance, low temperature performance, chemical resistance, solvent resistance and oil resistance can do.

The amino-containing siloxane is not particularly limited, and examples thereof include aminomethylpolydimethylsiloxane. The amount of the amino-containing siloxane used is preferably 3 to 10 parts by weight based on 100 parts by weight of the water-soluble polymer resin.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example 1]

A prepolymer resin having an NCO-terminal group was prepared by using 100 g of polyvinyl alcohol, 15 g of polyurethane, 5 g of polyethylene glycol, 15 g of alkoxysilane and IPDI (isophorone diisocyante) as starting materials. Then, DBTDL (dibutyltin dilaurate) and TEA ) And EDA (ethyl diamine), 5 g of silicon carbide having an average particle size of about 400 nm, 5 g of an alkyd resin and 100 g of propylene glycol monomethyl ether were mixed to prepare a coating composition for protecting a wafer.

[Example 2]

The procedure of Example 1 was repeated except that 15 g of polyurethane was replaced by 15 g of vinylpyrrolidone / methacrylamide / vinylimidazole copolymer.

[Example 3]

Was carried out in the same manner as in Example 1 except that 15 g of aminoethylpropane diol-acrylate copolymer was used instead of 15 g of polyurethane.

[Example 4]

The procedure of Example 1 was repeated, except that 3 g of modified starch ether was further added.

[Example 5]

The procedure of Example 1 was repeated except that 10 g of hydroxyethylcellulose was further added.

[Example 6]

The procedure of Example 1 was repeated except that 20 g of terephthalic acid metal salt was further added.

[Example 7]

The same procedure as in Example 1 was carried out except that 3 g of mineral oil was further added.

[Example 8]

The procedure of Example 1 was repeated except that 20 g of monomer (2-ethylhexyl acrylate) was further added.

[Example 9]

15 g of a polyphosphoric acid peeling inhibitor having a specific gravity of 1.0 or more and a viscosity at 60 ° C of 110 cPs was further added in the same manner as in Example 1.

[Example 10]

The procedure of Example 1 was repeated except that 4 g of tetraethylenepentamine was further added.

[Example 11]

5 g of octyltriethoxysilane having a molecular weight of about 300 Da was further added in the same manner as in Example 1.

[Example 12]

The procedure of Example 1 was repeated, except that 7 g of aminomethyl polydimethylsiloxane was further added.

[Comparative Example 1]

The procedure of Example 1 was repeated except that 15 g of polyurethane was excluded.

[Experiment]

The coating compositions prepared according to Examples 1 to 3 and Comparative Example 1 were measured on a wafer surface with an MST (Micro Scratch Tester) manufactured by CSM Instruments (Anton Paar).

The results are shown in Fig. 1 to Fig.

1 to 4, it was found that the surface adhesion and the strength of the surface of the coating composition for wafer protection according to the present invention as measured in Figs. 1 to 3 were significantly better than those in Fig. 4 in which the surface of Comparative Example 1 was measured I could.

As described above, those skilled in the art will understand that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are all illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention without departing from the spirit and scope of the present invention as defined by the appended claims and their equivalents.

Claims (4)

Based on 100 parts by weight of the water-soluble polymer resin,
Polyvinyl pyrrolidone / vinyl alcohol copolymer, poly (vinyl acetate-CO-crotonic acid), aminoethyl propanediol-acrylate copolymer, polyvinyl pyrrolidone / methacrylamide / vinyl imidazole copolymer, 5 to 50 parts by weight of a mixture thereof;
1 to 10 parts by weight of a surfactant;
5 to 30 parts by weight of a hydrolyzed silane compound;
10 to 30 parts by weight of a water-dispersed polyurethane dispersant;
3 to 10 parts by weight of nano-ceramic particles;
3 to 10 parts by weight of a binder; And
And 50 to 150 parts by weight of a solvent.
The method according to claim 1,
Wherein the water soluble polymer resin comprises polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyacrylic acid or a mixture thereof.
The method according to claim 1,
Wherein the surfactant is selected from the group consisting of polyethylene glycol, polyoxyalkylene glycol, polyethoxypropoxyalkyl glycol, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl ethers, polypropylene ethylene propylene copolymers, Protective coating composition.
The method according to claim 1,
Wherein the hydrolyzed silane compound is an alkoxysilane, silane oxide or a mixture thereof.

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