KR101334917B1 - Controlling method for contraction rate of curable resin, composition for curable resin controlable contraction rate, curable resin controlable contraction rate comprising the same, and manufacturing method by the same - Google Patents

Abstract

The present invention relates to a curable resin shrinkage control method, a curable resin composition controllable shrinkage rate, a shrinkage controllable curable resin comprising the same and a method for producing the same, by controlling the number of chain ends of the curable resin, to control the shrinkage of the curable resin It relates to a curable resin shrinkage control method.
The curable resin shrinkage control method according to the present invention can effectively control the shrinkage of the curable resin even if only a small amount of chain carriers by using a chain carrier that can be combined with a plurality of resins, the chain carrier is benzyl group, allyl group or pair By including at least one of the unsaturated system it is possible to block the progress of the side reaction, and to include the unsaturated compound in the chain carrier to maintain the properties that the resin is cured.

Description

Curable resin shrinkage control method, curable resin composition controllable shrinkage rate, shrinkable controllable curable resin comprising the same and a method for producing the same TECHNICAL MODE FOR CONTRACTION RATE OF CURABLE RESIN SAME, AND MANUFACTURING METHOD BY THE SAME}

The present invention relates to a curable resin shrinkage control method, a curable resin composition controllable shrinkage rate, a shrinkage controllable curable resin comprising the same, and a method for producing the same, more specifically, including a chain carrier that can be combined with a plurality of curable resins By controlling the shrinkage of the curable resin, fine patterns can be precisely formed, the surface energy of the curable resin can be reduced, and the curable resin shrinkage control method and shrinkage controllable curable resin can improve product quality. It relates to a composition and a shrinkage controllable curable resin comprising the same and a method for producing the same.

Recently, the development of lithography technology for mass production of semiconductor products such as DRAM has been made remarkably. Accordingly, research on various techniques for producing a pattern having a fine line width is being conducted. As one of the fine pattern manufacturing methods, a pattern is fabricated by selectively irradiating light onto a photoresist using a photomask. Photo-lithography technology has been developed, and many researches have been conducted to produce economical and mass-produced patterns, especially in the field of optical lithography. Techniques called Micro Injection Molding (MIM) and Step-and-Flash Imprint Lithography (SFIL) have been developed. These techniques have a common feature that allows resists to have a uniform pattern while applying a mold with an uneven surface directly to the resist.

Resins used in NIL, MIM, and SFIL are mainly resins cured by light or heat. This resin can have a stable pattern for chemical and mechanical etching as a mask and can be used for optical films, column spacers or color filters of LCDs.

However, if the mold is formed by applying a pressure to the mold and the resist is cured by applying light or heat to the resist, and the mold is separated, the resist does not fall well from the mold due to the shrinking action of the resist and the resist's own surface energy. There was a problem. As a result, the quality of the product is reduced when forming the fine pattern, the fine pattern cannot be manufactured precisely, and the resin is attached to the mold, resulting in shortening the life of the equipment. Accordingly, development of a curable resin having a low surface energy and a small shrinkage rate upon curing is required.

The present invention is to solve the above problems, by controlling the number of chain ends of the curable resin can control the shrinkage of the curable resin, a means for controlling the shrinkage rate using a chain carrier, comprising a chain carrier It is an object to provide a curable resin capable of shrinkage control.

By controlling the volume shrinkage rate when curing the curable resin by light or heat, the purpose of the present invention is to improve the accuracy of the fine pattern and to increase the reliability of the product, and to extend the service life of the mold used in manufacturing.

In addition, it is an object to be able to effectively produce a curable resin capable of shrinkage control by forming a stable radical intermediate in the curing step that proceeds to the radical reaction, and to prevent the generation of unnecessary substances.

In addition, the shrinkage controllable curable resin is intended to maintain the property to be cured by light or heat, and the purpose of being able to effectively control the shrinkage rate only by adding a small amount of chain carrier.

The present invention is to solve the above problems, the curable resin shrinkage rate control method of the present invention is made by adjusting the number of chain ends of the curable resin, the control of the number of chain ends of the curable resin chains that bind to a plurality of resins It is characterized by using a carrier.

The shrinkage controllable curable resin composition of the present invention comprises a chain carrier, the chain carrier comprising an unsaturated carbon unit and a plurality of chain conveying units, wherein the chain conveying unit is a benzyl group, an allyl group. group) or a conjugated? system group, wherein the chain transfer unit is characterized in that it comprises a sulfanylthiocarbonylsulfanyl group.

In addition, the unsaturated carbon unit comprises at least one of acryloyl group or a compound having an unsaturated carbon at the chain end, at least one of the chain carrier, the chain carrier is 0.1% by weight relative to 100% by weight of the curable resin composition % To 5.0% by weight.

The shrinkage controllable curable resin of the present invention is characterized in that a chain carrier is bonded to the curable resin, and the chain carrier comprises a chain transport unit and an unsaturated carbon unit.

In the method for producing a shrinkable controllable curable resin according to the present invention, a protecting group reaction step in which a hydroxyl group of a polyol reacts with a protecting group to produce a first compound, and a chain transfer unit reacting with a hydroxyl group of the first compound may be used. A chain transfer unit reaction step of producing a second compound, a protecting group removing step of removing the protecting group of the second compound to form a third compound, and a hydroxyl group of the third compound reacting with an unsaturated carbon unit to produce a fourth compound. Including the resulting unsaturated carbon unit reaction step, In the protecting group reaction step, at least two hydroxyl groups that do not react with the protecting group of the hydroxyl groups of the polyol is present, the fourth compound and the curable resin is reacted It further comprises a curable resin reaction step.

In the protecting group reaction step, the protecting group reacts with the hydroxyl group of the polyol to form an ether or acetal structure, and the protecting group adds 50 to 150 moles with respect to 100 moles of the polyol, and the polyol It is characterized by containing at least three hydroxyl groups.

Also in the chain transfer unit reaction step, the chain transfer unit comprises at least one of a benzyl group, an allyl group or a monounsaturated group, and in the protecting group removing step, the protecting group removing reaction proceeds under acidic conditions, the unsaturated In the carbon unit reaction step, the unsaturated carbon unit is characterized in that the acryloyl compound or unsaturated carbon at the chain end.

In addition, the protecting group reaction step, the chain transfer unit reaction step and the unsaturated carbon unit reaction step is characterized in that proceeds from -5 ℃ to 10 ℃.

According to the present invention, by controlling the shrinkage during curing of the curable resin using a chain carrier, it is possible to reduce the surface energy of the curable resin, thereby forming a more precise pattern, and improve the reliability of the produced product Not only that, but it also has the effect of maximizing the age of the mold.

The chain carrier may also be formed by selecting a compound comprising at least one of a benzyl group, an allyl group, a methylene group, or a conjugated unsaturated system to form a stable intermediate. It is possible to reduce side reactions and increase the yield of the desired material.

In the method for producing a curable resin capable of shrinkage control, the chain transfer unit can be prevented from chemically bonding to the excess polyol by reacting the protecting group in the first step, and the chain carrier is added to the curable resin by including an unsaturated carbon unit in the chain carrier. Even if there is an effect that can maintain the curability of the resin to the same extent as conventional.

In addition, by allowing a plurality of resins to bind to one molecule of the chain carrier, it is possible to effectively control the shrinkage rate even with a small amount of the chain carrier, thereby reducing the production cost and improving the quality of the resin and precisely manufacturing the fine patterns. It can be effective.

1 is a schematic diagram showing the degree of reduction of the number of chain ends before and after curing of the conventional curable resin
Figure 2 is a schematic diagram showing the degree of reduction of the number of chain ends before and after curing of the curable resin controllable shrinkage of the present invention
3 is a schematic diagram showing a process of bonding the curable resin and the chain carrier of the present invention.
Figure 4 is a flow chart sequentially showing a method for producing a curable resin shrinkage controllable of the present invention
5 is an apparatus for measuring the energy required to separate a mold from a resin, used in Examples and Comparative Examples.

When heat or light is applied to the curable resin, intermolecular bonds are formed, and solid polymers are formed. At this time, volume shrinkage of the curable resin occurs, and volume shrinkage of the curable resin is attributable to a decrease in the number of chain ends of the curable resin occupying a relatively large volume in the curable resin. Accordingly, the present invention discloses a method of controlling the extent to which the number of chain ends of the curable resin is reduced in order to control the volume shrinkage of the curable resin.

First, the shrinkage control method of the curable resin of the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a method of controlling the shrinkage ratio of the curable resin by adjusting the number of chain ends of the curable resin. Characterized in that it can be adjusted. 1 is a schematic diagram showing the degree of reduction of the number of chain ends before and after curing of the conventional curable resin, Figure 2 is a schematic diagram showing the degree of reduction of the number of chain ends of the curable resin according to the present invention. As shown in FIG. 1 and FIG. 2, according to the present invention, the degree of reduction in the number of chain ends of the curable resin before and after curing can be reduced, thereby controlling the shrinkage of the resin.

In addition, it is characterized in that to control the number of chain ends of the curable resin using a chain transfer agent (chain transfer agent) for coupling with a plurality of chains. By using a chain carrier that can combine with a plurality of chains, not only the use of a small amount of chain carriers can effectively control the degree of volume shrinkage before and after curing of the resin, but also reduce the cost required for carrying out the invention. can do.

Next, the shrinkage controllable curable resin composition of the present invention will be described in detail with the accompanying drawings.

The shrinkage controllable curable resin composition includes a chain carrier. The chain carrier comprises a chain transport unit and an unsaturated carbon unit. Formula 1 is an example of a chain carrier structure.

[Formula 1]

The parent of the chain carrier is a polyol, and the polyol is a molecule having at least three hydroxyl groups, which can be used without limitation, propanetriol (glycerol, glycerol), butanetriol, butanetriol (butanetetraol), pentanetriol, pentanetetraol, pentanepentaol, hexanetriol, hexanetetraol, hexanepentaol or hexanepentaol (hexanepentaol) hexanehexaol). In the above [Formula 1], the case of using glycerol as a parent was described as an example.

If the hydroxyl group of the polyol is less than three, there is a problem that the curing of the resin cannot easily occur, or a plurality of resins cannot be bonded to a chain carrier of one molecule, so that the shrinkage rate cannot be effectively controlled.

R1, R2 and R3 of [Formula 1] is a chain transfer unit or unsaturated carbon unit, the chain transfer unit is at least one of the following [Formula 1-1], unsaturated carbon unit is at least one of [Formula 1-2] One example is the case.

[Formula 1-1]

,

,

,

,

,

,

R is hydrogen or an alkyl group

[Formula 1-2]

,

n은 정수

,

n is an integer

The chain transport unit comprises at least one of a benzyl group, an allyl group or a conjugated π system group. The chain conveying unit is a part bonded to the chain carrier and means a unit to which the resin is substantially bonded in the chain carrier, and serves to control the shrinkage of the resin according to the present invention. Curable resins and chain carriers are driven by a radical reaction process. Since normal radicals are unstable species with short lifespans and very high reactivity, the unpaired electrons that form radicals must be delocalized to stabilize unstable radicals. do. Figure 3 is a schematic diagram showing the process of bonding the curable resin and the chain carrier of the present invention, the radical resin is formed (11) as the curable resin molecules are electrons escaped by light or heat, the radical 11 is a chain carrier The reaction proceeds sequentially with (20) to show a process in which a plurality of resins are bound to one chain carrier.

Therefore, it is preferable to select a compound in which the radical intermediate of the chain carrier, more specifically the radical intermediate of the chain carrier unit, which forms when the curable resin and the chain carrier proceed with reaction, forms a resonance structure so that the electrons can be delocalized, More preferably, it is effective to include at least one of a benzyl group, an allyl group, or a conjugated π system.

If the intermediate produced when the chain transfer unit reacts with the curable resin molecule does not form a resonance structure, not only can the radical reaction proceed stably, but also an unwanted side reaction occurs even if the reaction proceeds, or the chain carrier Due to the progress of the reaction between the curable resin molecules before the reaction with, it is not possible to achieve the object of the present invention called shrinkage control.

In addition, by using a strong electronegative sulfanyl-thiocarbonylsulfanyl group in the chain transport unit, the radical electrons formed can be delocalized to stabilize the radical intermediate of the chain carrier to facilitate the reaction. Can proceed. In addition, instead of the sulfur atom of the sulfanylthiocarbonylsulfanyl group, a group 16 element such as oxygen and selenium having a strong electronegativity may be selectively substituted.

There must be at least two chain transport units in the chain carrier. If there are less than two chain conveying units, only one resin can be bound per molecule of chain carrier, so that the volume shrinkage of the curable resin can not be effectively controlled, and the volume shrinkage rate is large so that a precise pattern cannot be formed. there is a problem.

It is also preferred that the unsaturated carbon unit of the chain carrier uses at least one of acryloyl groups or compounds with unsaturated carbon at the chain ends. The unsaturated carbon unit is a part bonded to the chain carrier, and the unsaturated carbon unit means that the curable unsaturated carbon is present at the end of the carbon chain, and polymerizes with other resin molecules upon curing. By introducing such an unsaturated carbon unit into the chain carrier can be cured by light or heat, the degree to which the resin before and after the chain carrier is cured can be maintained to the same degree.

At least one unsaturated carbon unit must be present, and when the unsaturated carbon unit is not present, there is a problem in that the resin is hardly cured and thus it is difficult to be used as a curable resin.

Next, look at the content ratio of the chain carrier.

The chain carrier is preferably from 0.1% to 5.0% by weight, more preferably from 0.2% to 3.0% by weight, most preferably from 0.3% to 1.0% by weight relative to 100% by weight of the curable resin composition capable of shrinkage control. Is effective.

When the chain carrier is less than 0.1% by weight relative to 100% by weight of the curable resin composition which can control the shrinkage rate, the chain carrier may not sufficiently exert its effect as a chain carrier, resulting in large volume shrinkage as in the case where no chain carrier is present. If a problem occurs and the amount exceeds 5.0% by weight, the shrinkage rate of the resin decreases in comparison with the increase in the content of the chain carrier, which reduces the product quality due to waste of material, increase in execution cost and increase of impurities. Will be imported.

Next, the curable resin which can control the shrinkage rate of the present invention is seen.

Curable resin which can control shrinkage rate is characterized by the chain carrier couple | bonded with normal curable resin. When heat or light is applied to the composition including the curable resin and the chain carrier, polymerization occurs due to a radical reaction. In the case of a conventional curable resin, a reaction between resins occurs as shown in FIG. In the case of the curable resin composition, the reaction proceeds between the resin and the chain carrier as shown in FIG. 3, so that the curable resin and the chain carrier are bonded.

The shrinkage controllable curable resin produced according to the present invention can effectively control the shrinkage of the curable resin by extending the mold life by minimizing the surface energy of the resin by combining a molecule of a chain carrier with a plurality of resins. As well as being able to control the shrinkage rate, there is an effect that can form a more precise pattern.

The chain carrier comprises a chain transport unit and an unsaturated carbon unit, wherein the chain transport unit and the unsaturated carbon unit are as described above.

Next, a method of manufacturing a curable resin capable of controlling shrinkage of the present invention will be described in detail with reference to the accompanying drawings.

As shown in Figure 4, the method for producing a shrinkage controllable curable resin according to the present invention is a protecting group reaction step (S10), chain transfer unit reaction step (S20), protecting group removal step (S30), unsaturated carbon unit reaction step ( S40) and the curable resin reaction step (S50) is made.

First, a protecting group reaction step (S10) is a step in which a hydroxyl group of a polyol reacts with a protecting group to generate a first compound, and a step for preventing an unnecessary reaction of a hydroxyl group of a polyol from proceeding. to be.

Through the protecting group reaction step (S10), as many chain transport units as desired can be bonded to the polyol, there is an effect that can be included in the chain carrier stably unsaturated carbon units.

As a protecting group for protecting the hydroxyl group, it is preferable to use a compound capable of reacting with the hydroxyl group to form an ether or acetal structure, more preferably 3,4-dihydro-2H- Pyran (DHP) or silyl ether protectors are effective. A protecting group means a substance used to protect a functional group when the reactant has a functional group that does not withstand the reaction conditions required for any modification, and in the present invention, a protecting group is used to protect the hydroxyl group of the polyol.

The ether and acetal present in the first compound produced through the protecting group reaction step (S10) are relatively low in reactivity compared to alcohol, are relatively stable, do not decompose under basic conditions, and can be easily separated into compounds before the reaction under acidic conditions. By using the properties of the ether and acetal, it is possible to protect the hydroxyl group from a relatively reactive reactive group through a protecting group so that unnecessary reactions do not occur, and the protecting group can be easily removed if necessary.

 The DHP and silyl ether protecting groups are as shown in the following [Formula 2].

(2)

,

R₁, R₂ 및 R₃는 H 또는 알킬기

,

R ₁ , R ₂ and R ₃ are H or an alkyl group

In the case of using DHP as a protecting group in the protecting group reaction step (S10), DHP forms acetal through a nucleophilic addition reaction with a hydroxyl group, and when using a silyl ether protecting group as the protecting group, An electrophilic substitution reaction is caused by oxygen, and the leaving group is released to form a silyl ether bond.

As the leaving group present in the silyl ether protecting group, it is preferable to use an atom or molecule having a large electronegativity, and more preferably, a halogen group element is used. R ₁ , R ₂ and R ₃ may be used in any combination of H or alkyl groups, but is preferably H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl, tert -butyl, and more. Preferably, R ₁ and R ₂ are methyl _and R ₃ is tert- butyl.

In the protecting group reaction step (S10), at least two hydroxyl groups which do not react with the protecting group among the hydroxyl groups of the polyol should be present. When there are less than two hydroxyl groups that do not react with the protecting group, there is no chain transport unit or only one chain transport unit in one molecule of chain carrier, so that the volume shrinkage of the resin is large and the shrinkage rate can be effectively controlled. There is a problem in that it is impossible to carry out the object of the present invention.

In the protecting group reaction step (S10), the protecting group is preferably added 50 mol to 150 mol with respect to 100 mol of the polyol, more preferably 60 mol to 130 mol, and most preferably 70 mol to 120 mol. to be.

When the protecting group is added to less than 50 moles with respect to 100 moles of the polyol, the hydroxyl groups of the polyol may not be sufficiently protected, so that the unsaturated carbon unit may not react in the following unsaturated carbon unit reaction step (S40). Since the property to be hardened is poor, there is a problem in using it as a curable resin. On the other hand, when the protecting group is added in excess of 150 moles with respect to 100 moles of polyol, the hydroxyl groups of the polyol are excessively protected so that the chain transport unit does not react with the hydroxyl groups of the polyol in the following chain transport unit reaction step (S20). It becomes impossible to achieve the objective of this invention called shrinkage control of curable resin.

In the protecting group reaction step (S10), the polyol should have at least three hydroxyl groups, and the description thereof is the same as described above with respect to [Formula 1].

As the solvent in the protecting group reaction step (S10), water may be used, and as the organic solvent, organic solvents such as alcohols, acetates, ethers, glycols, ketones, and carbonates, dimethylformaldehyde (DMF), Any one of aprotic polar organic solvents such as tetrahydrofuran (THF) and N, N-dimethylacetamide (DMAc) may be used alone or in combination of two or more thereof. Preferably, dimethylformaldehyde and tetrahydro are used. Use furan mixed.

The polyol and the protecting group and sulfonic acid monohydrate are added to the above solvent and stirred at -5 ° C to 10 ° C for 1 to 4 hours. Thereafter, the mixture was washed with sodium hydrogen carbonate (NaHCO ₃ ), the ethyl acetate and the solvent were evaporated, and the first compound was separated by chromatography.

The chain transfer unit reaction step (S20) is a step in which the chain transfer unit reacts with the hydroxyl group of the first compound to generate a second compound.

Through the chain transfer unit reaction step (S20), it is possible to form a position at which the resin can be bonded to the chain carrier, and the contraction rate control can be effectively performed by reacting the plurality of chain transfer units with the first compound.

In the chain transfer unit reaction step (S20), the chain transfer unit includes at least one of a benzyl group, an allyl group, or a monounsaturated group group, and the description thereof is the same as that of the chain transfer unit.

In the chain transfer unit reaction step (S20), an ester or ether bond is formed between the first compound and the chain transfer unit. If the chain transfer unit contains carboxylic acid derivatives such as acyl halides, acid anhydrides, nitriles, amides, etc., the hydroxyl groups of the polyols and the nucleophilic addition-removal reactions are When the ester is formed, and the chain transport unit includes a functional group capable of acting as a leaving group such as an alcohol or a halide, ether is formed through a nucleophilic substitution reaction with a hydroxyl group of the polyol.

In the esterification reaction, the reaction may proceed in both acid or base conditions, and esters are produced by Fischer esterification under acidic conditions and saponification under basic conditions. Meanwhile, during the etherification reaction, the reaction may proceed under an acid catalyst, and particularly, in the case of asymmetric ether synthesis, a Williamson ether synthesis method may be used.

Preferably, esterification is used, methane dichloride (CH ₂ Cl ₂ ) is used as the solvent, and it is effective to proceed with the Steglich esterification reaction using DCC and DMAP. A general scheme of the Steglich esterification reaction is shown in the following [Formula 3].

(3)

As a solvent of the chain transfer unit reaction step (S20), water may be used, and as an organic solvent, organic solvents such as alcohols, acetates, ethers, glycols, ketones, and carbonates, or dimethylformaldehyde (DMF) ), Tetrahydrofuran (THF), N, N- dimethylacetamide (DMAc) and the like can be used either alone or in combination of two or more.

The chain transfer unit reaction step (S20) preferably adds the first compound and the chain transfer unit in a solvent of methane dichloride (CH ₂ Cl ₂ ) and in the presence of DCC and DMAP for 1 to 5 hours at -5 ° C to 10 ° C. After stirring for a while, it is effective to filter out impurities using a precipitation method, to evaporate the solvent, and to separate the second compound using chromatography or the like.

The protecting group removing step (S30) is a step of removing the protecting group of the second compound, and corresponds to a reverse reaction of the protecting group reaction step (S10).

By removing the protecting group through the protecting group removing step (S30) and restoring the hydroxyl group, it becomes possible to bind the unsaturated carbon unit which is necessary as a chain carrier. If this step is not present, there is a problem in that the unsaturated carbon unit is not bonded to the chain carrier, resulting in a weak curability of the resin. Therefore, the protecting group can be separated from the second compound by adding an acid to the second compound, and the hydroxyl group can be recovered to the second compound, followed by the unsaturated carbon unit reaction step (S40).

The protecting group removal proceeds under acidic conditions. Since acetal is a kind of ether, neither acetal nor ether is easily decomposed under basic conditions, and the protecting group can be easily separated under acidic conditions.

As a solvent of the protecting group removing step (S30), water may be used, or as an organic solvent, an organic solvent such as alcohol, acetate, ether, glycol, ketone, and carbonate, or dimethyl formaldehyde (DMF) And aprotic polar organic solvents such as tetrahydrofuran (THF) and N, N-dimethylacetamide (DMAc) may be used alone or in combination of two or more thereof, preferably THF and methanol may be mixed. It is effective to use.

The protecting group can be separated from the second compound by adding an acid to the above solvent and then stirring. As the acid in the reaction, acid may be used for all kinds of commonly used hydrochloric acid, sulfuric acid, phosphoric acid, and the like. After washing with sodium hydrogen carbonate or the like, only the third compound is separated by chromatography.

The unsaturated compound reaction step (S40) is a step in which the hydroxyl group of the third compound and the unsaturated carbon unit react to generate a fourth compound.

Through the unsaturated compound reaction step (S40), a polymerizable position can be introduced into the chain carrier, and as a result, the curability of the resin including the chain carrier can be maintained to a level equivalent to that of the conventional resin.

The unsaturated carbon unit is effective when the acryloyl compound (CH ₂ CRCO—, R is H or an alkyl group) or a compound having unsaturated carbon at the chain end. As the compound having an unsaturated carbon at the chain end, a functional group capable of reacting with a hydroxyl group of a polyol such as a halide, an alcohol, a carboxylic acid derivative, a carboxylic acid to form an ether or an ester can be used, and in this case, the hydride of the polyol The reaction with the hydroxyl group forms an ether or ester bond. On the other hand, the acryloyl compound reacts with the hydroxyl group of the polyol to form an ester bond.

As a solvent of the unsaturated carbon unit reaction step (S40), water may be used, or as an organic solvent, organic solvents such as alcohols, acetates, ethers, glycols, ketones, and carbonates, or dimethyl formaldehyde ( Any one of aprotic polar organic solvents such as DMF), tetrahydrofuran (THF) and N, N-dimethylacetamide (DMAc) may be used alone or in combination of two or more thereof.

In the above solvent, triethylamine and the third compound are stirred together with an unsaturated compound or acryloyl compound at -5 ° C to 10 ° C for 1 to 4 hours. Thereafter, the chlorinated ammonium solution is washed and the fourth compound is separated by chromatography.

Curable resin reaction step (S50) is a step in which the fourth compound and the curable resin reacts, will be described with reference to FIG. Curable resin reaction step (S50) is a step in which the fourth compound, that is, the chain carrier 20 and the curable resin molecules are bonded, the reaction proceeds by a radical reaction. Radicals are formed on the curable resin molecules (11) by light or heat, and the radicals undergo a chain reaction by the chain carriers (20) with radicals, whereby a plurality of curable resin molecules are bonded to the chain carriers of one molecule (33). Done.

Hereinafter, through one embodiment of the composition for shrinkage control according to the present invention, to demonstrate the effect of the present invention.

Example  One

In the present invention, the following [Formula 4] (hereinafter LS-UV30) is used as the curable resin.

[Formula 4]

[Formula 5] is an example for the protecting group reaction step (S10) to unsaturated carbon unit reaction step (S40).

[Chemical Formula 5]

Thin DHP, pTsOH.H ₂ O, DMF / THF, 0 ° C, 2 hours

Ii is DCC, DMAP, CH ₂ Cl ₂ , 0 ° C., 3 hours

Thin HCl, THF / CH ₃ OH

Cry acrylol chloride, triethylamine, CH ₂ Cl ₂ , 0 ℃, 2 hours

In the protecting group reaction step (S10), the protecting group was 3,4-dihydro-2H-pyran (DHP), and the polyol was glycerol. 10 g (108.6 mmol) of glycerol was added to DMF / THF (1 mL / 25 mL), and 7.5 mL (82.7 mmol) of 3,4-dihydro-2H-pyran (DHP) and 0.16 g of p-toluene sulfonic acid monohydrate were added to the solution. 0.8 mmol) is added and stirred at 0 ° C. for 2 h. After washing with NaHCO ₃ solution, and evaporated NaHCO ₃ with ethyl acetate and solvent in vacuo and the first compound is separated by silica gel column chromatography.

In the chain transfer unit reaction step (S20), 3-benzylsulfanyl-thiocarbonylsulfanyl propionic acid (BSCS) was used as the chain transfer unit. To 3 g (14.1 mmol) of the first compound solution, 6.1 g (29.6 mmol) of DCC, 0.09 g (0.7 mmol) of DMAP, and 7.68 g (28.2 mmol) of BSCS were added to 20 mL of CH ₂ Cl ₂ , followed by stirring at 0 ° C. for 3 hours. Pour hexane to allow the reaction composition to precipitate and filter out the resulting urea. After evaporation of the solvent, the second compound is separated by silica gel column chromatography.

In the protecting group removal step (S30), 8.5 g (12.4 mmol) of the second compound was stirred with 5 mL of 2N HCl under THF / CH3OH (10 mL / 10 mL) to remove the protecting group, and the mixture was washed with NaHCO ₃ solution, and then ethyl acetate. Extract with. The third compound is then separated by silica gel column chromatography.

As the unsaturated compound reaction step (S40), acryloyl chloride was used as the unsaturated compound. To 30 mL of CH ₂ Cl ₂ and 2.8 mL (20 mmol) of triethylamine, 5.8 g (9.7 mmol) of the third compound and 0.96 mL (11.9 mmol) of acryloyl chloride were added and stirred at 0 ° C. The mixture is washed with NH ₄ Cl and extracted with ethyl acetate. Thereafter, the fourth compound (MC4) is separated through silica gel column chromatography.

0.3 wt% of the fourth compound prepared in the same manner as above was added to LS-30UV based on 100 wt% of LS-30UV.

Example  2

All other conditions were the same, and in Example 1, the amount of the fourth compound was changed to 0.6% by weight based on 100% by weight of LS-30UV.

Comparative Example

All other conditions were the same and changed in Example 1 without adding the fourth compound.

The resins of the above Examples 1, 2 and Comparative Examples are treated with ultraviolet rays to cure the resin, and the volume shrinkage rates before and after curing are compared. Also, as shown in FIG. 5, a load cell capable of measuring a resolution of 0.01 N up to 50 N in a mold having a copper and brass ratio of 6: 4 is installed on the mold to separate the mold from the resin. Measured. When measuring the force required to remove the mold, the average value was recorded by repeating the test several times except the case where the resin was broken in order to reduce the error.

Table 1 below shows the volume change before and after UV curing of Examples 1, 2 and Comparative Examples and the magnitude of force required to separate the mold from the resin.

Volume (cm ³ / g) % Change in volume Force for Mold Separation (Kg _f ) Before UV Curing After UV curing Example 1 0.746 0.605 18.9 - Example 2 0.750 0.679 9.5 0.15 Comparative Example 0.744 0.560 24.7 0.28

As shown in Table 1, in Example 1 and Example 2, the volume change before and after hardening is small compared with the comparative example. In addition, in the case of Example 2, where the fourth compound content is higher than that in Example 1, the volume change before and after curing is smaller. And it can be seen that the force required to separate the mold from the resin in the case of Example 2 compared to the comparative example is smaller.

Therefore, based on the above data, it can be seen that the curable resin shrinkage rate control composition comprising the chain carrier according to the present invention can reduce the shrinkage rate and surface energy of the resin as compared with the prior art.

Through this, by controlling the addition ratio of the curable resin and the fourth compound as a chain carrier, it is possible to control the degree of change in shrinkage before and after curing of the curable resin, and at the same time, the magnitude of the force required to separate the mold from the resin. It can also be reduced and can be preferably applied as a curable resin capable of shrinkage control capable of precisely forming a fine pattern.

The present invention has been described in detail with reference to preferred embodiments thereof. However, the scope of the present invention is not limited to the above embodiments, but may be embodied in various forms of embodiments within the scope of the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.

10: curable resin
11: curable resin radical
20: chain carrier
30: cured resin
31: chain carrier in which a plurality of curable resins are bound
100: curable resin
200: cured resin

Claims (20)

By controlling the reduction of the number of chain ends after curing of the curable resin using a chain carrier capable of bonding with a plurality of resins, the reduction of the shrinkage of the curable resin is controlled,
The parent of the chain carrier is a polyol having at least three hydroxyl groups, at least one of the hydroxyl groups of the polyol has an unsaturated carbon unit bonded thereto, and at least two hydroxyl groups have a chain transport unit bonded thereto. Curable resin shrinkage control method
delete Including chain carriers,
The parent of the chain carrier is a polyol having at least three hydroxyl groups, at least one of the hydroxyl groups of the polyol has an unsaturated carbon unit bonded thereto, and at least two hydroxyl groups have a chain transport unit bonded thereto. Curable resin composition which can control shrinkage rate
The method of claim 3, wherein
The chain transfer unit comprises at least one of a benzyl group, an allyl group, or a conjugated π system group, and the shrinkage controllable curable resin composition
5. The method of claim 4,
The chain transfer unit comprises a sulfanylthiocarbonylsulfanyl group, the shrinkage controllable curable resin composition, characterized in that
The method of claim 3, wherein
The unsaturated carbon unit is a shrinkage controllable curable resin composition characterized in that it comprises at least one of acryloyl group or a compound having an unsaturated carbon at the chain end
The method according to claim 6,
At least one unsaturated carbon unit is included in the chain carrier, shrinkage controllable curable resin composition, characterized in that
The method of claim 3, wherein
The chain carrier is shrinkage controllable curable resin composition, characterized in that from 0.1% to 5.0% by weight relative to 100% by weight of the curable resin composition.
delete A chain carrier is bonded to the curable resin, and the parent of the chain carrier is a polyol having at least three hydroxyl groups, at least one of the hydroxyl groups of the polyol has an unsaturated carbon unit bonded thereto, and at least two hydroxyl groups. The shrinkage controllable curable resin, characterized in that the chain conveying unit is coupled to the
delete A protecting group reaction step in which a hydroxyl group of the polyol reacts with a protecting group to generate a first compound;
A chain transfer unit reaction step of reacting a chain transfer unit with a hydroxyl group of the first compound to generate a second compound;
A protecting group removing step of removing the protecting group of the second compound to produce a third compound; And
And a unsaturated carbon unit reaction step of reacting the hydroxyl group of the third compound with an unsaturated carbon unit to produce a fourth compound.
In the protecting group reaction step, at least two hydroxyl groups which do not react with the protecting group among the hydroxyl groups of the polyol are present in the shrinkage controllable curable resin manufacturing method
13. The method of claim 12,
The curable resin reaction step of reacting the fourth compound and the curable resin; Curable resin manufacturing method characterized in that it further comprises
The method according to claim 12 or 13,
In the protecting group reaction step, the protecting group reacts with the hydroxyl group of the polyol and then forms an ether or acetal structure.
13. The method of claim 12,
In the protecting group reaction step, the protecting group is a shrinkage controllable curable resin manufacturing method characterized in that 50 to 150 moles are added to 100 mol of the polyol.
The method according to claim 12 or 13,
In the protecting group reaction step, the polyol has at least three hydroxyl groups, characterized in that the shrinkage controllable curable resin manufacturing method
The method according to claim 12 or 13,
In the chain conveying unit reaction step, the chain conveying unit comprises at least one of a benzyl group, an allyl group, or a monounsaturated group.
The method according to claim 12 or 13,
The protecting group removing step, the shrinkage controllable curable resin manufacturing method characterized in that the progress under acidic conditions
The method according to claim 12 or 13,
In the unsaturated carbon unit reaction step, the unsaturated carbon unit is a method for producing a shrinkage controllable curable resin, characterized in that the acryloyl compound or an unsaturated carbon at the chain end
The method according to claim 12 or 13,
The protecting group reaction step, the chain transfer unit reaction step and the unsaturated carbon unit reaction step is a shrinkage controllable curable resin manufacturing method characterized in that proceeds under -5 ℃ to 10 ℃

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