KR20040074390A - Uv curing type release coating oligomer - Google Patents

Abstract

PURPOSE: Provided is a UV curable-type release coating oligomer, which has mainly acrylic groups to completely control its UV cure and is economically advantageous over silicone compound. CONSTITUTION: The UV curable-type release coating oligomer is represented by formula I, wherein Y is O or NH group and Z is a residue of a compound of formula III, IV or V, except a leaving group(H); and is prepared by reacting a compound of formula II having many isocyanate groups with a compound of formula III: R1-CH2OH or formula IV having a UV curable group and optionally a compound of formula V having a releasing group. The UV curable-type release coating oligomer of formula I having 1 or 2 of UV curable groups and the UV curable-type functional acrylic oligomer of formula I having 3 of UV curable groups are combined with a multifunctional acrylate monomer, a photoinitiator and any additives to prepare a UV curable-type release coating agent.

Description

UV curable release coating oligomer {UV CURING TYPE RELEASE COATING OLIGOMER}

The present invention relates to a UV curable release coating oligomer, and more particularly to a urethane-based UV curable release coating oligomer having a UV curing functional group.

In general, thermosetting silicones have a disadvantage in that peeling strength decreases over time due to incomplete curing of the silicone material after curing as compared to UV curing silicones, leaving residues (residues) on the adhered surface after the coating treatment. In addition, the application of a peel-coated product using a thermosetting silicone to a sophisticated product such as electrical, electronic, etc. has a fatal disadvantage of providing a cause of contamination due to such residue.

In addition, UV-curable oligomers containing silicones synthesized for peel coating, although they contain acrylic groups, tend to not completely cure during UV curing since the basic composition is silicone.

In order to overcome this problem, in order to overcome this problem, the functionalized UV curable base oligomer containing all acrylic groups can be synthesized, and the UV curing can be perfectly controlled by combining with the peelable UV curable oligomer, and in terms of economical cost, It can be reduced to a minimum.

Accordingly, an object of the present invention is to provide a new urethane-based UV curable release coating oligomer which can solve the problems of the conventional thermosetting and UV curable release coating materials as described above.

In order to solve the above object, the present invention provides a novel UV-curable release coating oligomer represented by the following formula (I).

Formula I

Wherein Y represents an O or NH group and Z represents a moiety excluding the leaving group (H) of the compound of Formula III, Formula IV or Formula V.

Formula III

R ¹ -CH ₂ OH

Wherein R ¹ represents H ₂ C═CHCOOCH ₂ CH ₂ or (H ₂ C═CHCOOCH ₂ ) ₃ C)

Formula IV

(Wherein R ² represents hydrogen or a methyl group and l represents an integer of 1 to 6)

Formula V

(Where X represents an OH or NH ₂ group, m represents an integer from 1 to 10, and n represents an integer from 10, 30 or 70)

The UV curable release coating oligomer of formula (I) is prepared by reacting a compound of formula (III) or formula (IV) having a UV curable group with a compound of formula (V) having a peelable group to the following compound (II) containing the most isocyanate functional groups.

Formula II

In addition, the UV curable release coating oligomer of formula (I) may be prepared by reacting the compound of formula (III) or formula (IV) having a UV curable group with the compound of formula (II) containing the most isocyanate functional groups.

In the above reaction, dibutyl tin dilaurate may be added to catalyze.

Also in the present invention, 3 to 4% by weight of the UV curable release coating oligomer of formula (I) having 1 to 2 UV curable groups, 40 to 50% by weight of functional UV curable acrylic oligomer of formula (I) having three UV curable groups, Provided is a UV curable release coating agent containing 40 to 45% by weight of a multifunctional acrylate monomer.

The UV curable release coating oligomer represented by Chemical Formula I obtained in the present invention is a urethane-based UV curable material. Chemically, urethane is synthesized by reaction with functional groups that can easily react with isocyanate groups, and UV curing functional groups are added to synthesize a UV curable release coating material.

Compound III or Compound IV used in the present invention has a UV-curable group, Compound V is a compound having a peelable group, the present invention is a compound III or a compound to each of the three isocyanate groups It is characterized by introducing the UV curable group from IV or the peelable group from compound V to obtain the target compound I having UV curability and peelability.

In the present invention, UV curable groups are introduced into at least one isocyanate group of compound II.

Dibutyltin dilaurate (CH ₃ (CH ₂ ) ₁₀ COO] ₂ Sn [(CH ₂ ) ₃ CH ₃ ] ₂ ) is used in the reaction of the present invention.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example

(Synthesis of UV Curable Peel Coating Oligomers)

Example 1

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 1.0 mole of Formula V compound (X = OH, n = 10) is added dropwise through a dropping funnel for about 1 hour. After dropping, the mixture was stirred for 8 hours at room temperature, and 2.0 moles of the compound of formula III (R ¹ is H ₂ C = CHCOOCH ₂ CH ₂ ) were added dropwise to the dropping funnel at room temperature over 1 hour. After stirring for 8 hours at room temperature, the reaction was terminated to obtain the title compound (I).

In the same manner as above, 1.0 mole of the compound of Formula V (X = OH, n = 30 or 70) was used, and the compound of Formula III (R ¹ represents (H ₂ C = CHCOOCH ₂ ) ₃ ) or the compound of Formula IV was 2.0, respectively. The compound I was obtained using molar.

Example 2

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 1.0 mole of Formula V compound (X = NH ₂ , n = 10) is added dropwise through a funnel for about 1 hour. After dropping, the mixture was stirred for 8 hours at room temperature, and 2.0 moles of the compound of formula III (R ¹ is H ₂ C = CHCOOCH ₂ CH ₂ ) were added dropwise to the dropping funnel at room temperature over 1 hour. After stirring for 8 hours at room temperature, the reaction was terminated to obtain the title compound (I).

In the same manner as above, 1.0 mole of the compound of Formula V (X = NH ₂ , n = 30 or 70) was used, and the compound of Formula III (R ¹ represents (H ₂ C = CHCOOCH ₂ ) ₃ ) or the compound of Formula IV, respectively. The compound I was obtained using 2.0 mol.

Example 3

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 2.0 moles of the compound (V) (X = OH, n = 10) are added dropwise via a dropping funnel for about 1 hour. After dropping, the mixture was stirred at room temperature for 8 hours, and 1.0 mole of the compound of formula III (R ¹ is H ₂ C = CHCOOCH ₂ CH ₂ ) was added dropwise to the dropping funnel at room temperature over 1 hour. After stirring for 8 hours at room temperature, the reaction was terminated to obtain the title compound (I).

In the same manner as above, 2.0 moles of the compound of Formula V (X = OH, n = 30 or 70) are used, respectively, and the compound of Formula III (R ¹ represents (H ₂ C = CHCOOCH ₂ ) ₃ ) or the compound of Formula IV is 1.0, respectively. The compound I was obtained using molar.

Example 4

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 2.0 moles of the compound of Formula V (X = NH ₂ , n = 10) are added dropwise through the funnel for about 1 hour. After dropping, the mixture was stirred at room temperature for 8 hours, and 1.0 mole of the compound of formula III (R ¹ is H ₂ C = CHCOOCH ₂ CH ₂ ) was added dropwise to the dropping funnel at room temperature over 1 hour. After stirring for 8 hours at room temperature, the reaction was terminated to obtain the title compound (I).

In the same manner as above, 2.0 moles of the compound of Formula V (X = NH ₂ , n = 30 or 70) are used, and the compound of Formula III (R ¹ represents (H ₂ C = CHCOOCH ₂ ) ₃ ) or the compound of Formula IV, respectively. The compound I was obtained using 1.0 mole.

(Synthesis of Functional UV Curable Acrylic Oligomers)

Example 5

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. To the dropping funnel, 894 g (3.0 mol) of formula III compound (R ¹ is (H ₂ C = CHCOOCH ₂ ) ₃ ) are added dropwise slowly over 1 hour at room temperature. This reaction is exothermic and generates a large amount of heat, so be careful to add dropwise. After stirring for 20 hours at room temperature, the reaction was terminated to obtain the title compound (I).

Example 6

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 130 g (1.0 mole) of Formula III compound (R ¹ is H ₂ C = CHCOOCH ₂ CH ₂ ) was added dropwise to the dropping funnel at room temperature over 1 hour. This reaction is exothermic and generates a large amount of heat, so be careful to add dropwise. After the dropwise addition, after stirring for 5 hours at room temperature, 569 g (2.0 mol) of formula III compound (R ¹ is (H ₂ C = CHCOOCH ₂ ) ₃ ) was added dropwise through a dropping funnel for about 1 hour, and then at room temperature for 24 hours. After stirring, the reaction was terminated to obtain the title compound (I).

Example 7

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 1.0 mole of the compound of formula IV (R ² is H) was added dropwise to the dropping funnel at room temperature over 1 hour. This reaction is exothermic and generates a large amount of heat, so be careful to add dropwise. After the dropwise addition, after stirring for 5 hours at room temperature, 569 g (2.0 mol) of formula III compound (R ¹ is (H ₂ C = CHCOOCH ₂ ) ₃ ) was added dropwise through a dropping funnel for about 1 hour, and then at room temperature for 24 hours. After stirring, the reaction was terminated to obtain the title compound (I).

Example 8

In a three neck flask equipped with a mechanical stirrer, 594 g (3 NCO) of a compound of formula II was added and 1.0 g of dibutyltin dilaurate was added. 1.0 mole of the compound of Formula IV (R ² is CH ₃ ) was added to the dropping funnel and slowly added dropwise at room temperature over 1 hour. This reaction is exothermic and generates a large amount of heat, so be careful to add dropwise. After the dropwise addition, after stirring for 5 hours at room temperature, 569 g (2.0 mol) of formula III compound (R ¹ is (H ₂ C = CHCOOCH ₂ ) ₃ ) was added dropwise through a dropping funnel for about 1 hour, and then at room temperature for 24 hours After stirring, the reaction was terminated to obtain the title compound (I).

Formulation example

The combination of the synthesized UV curable release coating oligomers (Examples 1 to 4) and functional UV curable base oligomers (Examples 5 to 8) yielded a complete UV curable release coating agent. Basic formulations include multifunctional acrylate monomers, photoinitiators and some additives in addition to the two types of oligomers. The multifunctional acrylate monomer plays a role of itself as a linker during UV curing so that acrylate functional groups present in the UV release coating agent easily participate in UV curing.

The actual silicone content contained in the general silicone base release coating agent is about 3 to 4%, and considering the economical efficiency, it is known that this amount is sufficient to exhibit sufficient peelability after coating. Table 1 shows the basic formulation for the UV-curable release coating carried out in the present invention.

Table 1 Example of Basic Formulation of UV Curable Peeling Coating

Furtherance weight% UV Curing Peeling Coating Oligomer (Examples 1 to 4) 3 to 4 Functional UV Curable Acrylic Oligomer (Examples 5 to 8) 40-50 Multifunctional Acrylate Monomer 40 to 45 Photoinitiator 4 to 5 Additive 0.1 to 0.3 all 100

As the multifunctional acrylate monomer, the most economical pentaerythritol triacrylate (PETA) was used after preliminary experiments. Several kinds of photoinitiators for initiating the radical polymerization reaction used for UV curing are known and have shown satisfactory results as a result of experiments. In the present invention, 1-hydroxy-cyclohexylphenyl ketone is the most easily available and economical. (Trade name; Igacure 184, manufactured by Ciba-Geigy Co., Ltd.). Moreover, benzopinone can be used as an additive.

UV Curing and Curing Conditions

UV-curable release coating agent, a functional acrylic UV oligomer, a crosslinking agent and a photoinitiator (Igacure 184) 4 to 5% (w / w) were added and mixed as shown in Table 1 above, followed by a Meyer Bar Coater. # 3 was used to coat on kraft paper (20 cm × 20 cm) to a thickness of about 3-4 μm (after curing). The coated kraft paper was dried in a 40 ° C. oven for 30 seconds, and then immediately using a UV lamp (80 watt / cm 2 medium pressure mercury lamp), a line speed of 10 m / min, UV dose ( The dose was set to 800-1000 mJ / cm 2 with IL390B Light bugradiometer manufactured by International Light, and passed until there was no tacky.

Measurement of residue on the surface of UV peel coating

After UV curing, the surface of the kraft paper is rubbed by hand to determine whether the resulting coating film is completely cured by UV (visual test). Alternatively, the residue remaining during peeling after UV coating was measured by applying coated kraft paper to a glass substrate of 3 cm in width and length, and left for 24 hours under a load of about 5 kg, removing the kraft paper, and depositing gold on the glass substrate. After measuring the degree of UV curing can be confirmed by measuring the SEM and whether or not the residue remaining on the surface.

SEM photograph of the adherend after UV curing peeling

As described above, according to the present invention, the UV curing can be perfectly controlled by combining the functional UV curable basic oligomer containing all acrylic groups and combining with the peelable UV curable oligomer, which is also expensive in terms of economics. The silicone compound can be reduced to a minimum.

Claims (9)

A novel UV curable release coating oligomer represented by formula (I). Formula I Wherein Y represents an O or NH group and Z represents a moiety excluding the leaving group (H) of the compound of Formula III, Formula IV or Formula V. Formula III R ¹ -CH ₂ OH Wherein R ¹ represents H ₂ C═CHCOOCH ₂ CH ₂ or (H ₂ C═CHCOOCH ₂ ) ₃ C) Formula IV (Wherein R ² represents hydrogen or a methyl group and l represents an integer of 1 to 6) Formula V (Where X represents an OH or NH ₂ group, m represents an integer from 1 to 10, and n represents an integer from 10, 30 or 70) The UV curable release coating oligomer according to claim 1, wherein the compound of formula (I) has one release coating group of formula (III) or formula (IV). The UV curable release coating oligomer of claim 1, wherein the compound of Formula I has two release coating groups of Formula III or Formula IV. The UV curable release coating oligomer according to claim 1, wherein the compound of Formula I has three release coating groups of Formula III or Formula IV. A method for preparing a compound of formula I by reacting a compound of formula III or IV having a UV curable group with a compound of formula V having a strippable group to a compound of formula II containing the most isocyanate functional groups. Formula II A method of preparing a compound of formula I by reacting a compound of formula II or formula IV having a UV curable group with a compound of formula II containing the most isocyanate functional groups. 7. Process according to claim 5 or 6, wherein dibutyltindilaurate is added. 3 to 4% by weight of UV curable release coating oligomer of formula (I) having 1 to 2 UV curable groups, 40 to 50% by weight of functional UV curable acrylic oligomer of formula (I) having 3 UV curable groups, multifunctional acrylate monomer UV-curable release coating agent containing 40 to 45% by weight. The UV curable release coating agent according to claim 8, further comprising 4-5 wt% of a photoinitiator and 0.1-0.3 wt% of an additive.