KR102504363B1 - Silicone based release composition and release film having release layer cured therefrom - Google Patents

Abstract

상기 화학식 1에서,
R은 아크릴계 단량체로 된 중합단위이고,
R₁ 및 R₂는 각각 독립적으로 수소, 탄소수가 1 내지 10인 알킬기 또는 알케닐기이고,
x는 1 내지 1,000의 정수이고,
y는 1 내지 1,000의 정수이다.
본 발명의 실리콘계 이형제 조성물로 형성된 이형층은 피착체 코팅시 피착체에 대한 젖음성이 양호하며 피착체에 대한 적절한 박리력을 유지할 수 있다. The present invention is a silicone-based release agent composition comprising a silicone-based release resin and a crosslinking agent, characterized in that it further comprises a compound represented by Formula 1 below:
<Formula 1>

In Formula 1,
R is a polymerization unit made of an acrylic monomer,
R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group;
x is an integer from 1 to 1,000;
y is an integer from 1 to 1,000.
The release layer formed of the silicone-based release agent composition of the present invention has good wettability to the adherend when coating the adherend and can maintain appropriate peeling force on the adherend.

Description

Silicone-based release agent composition, release film having a release layer cured therefrom {SILICONE BASED RELEASE COMPOSITION AND RELEASE FILM HAVING RELEASE LAYER CURED THEREFROM}

The present invention relates to a silicone-based release agent composition formed of a release film that has adhesiveness to an adherend and is easily removable from the adherend, and a release film having a release layer cured therefrom.

The release film is used in various fields such as liquid crystal displays, plasma displays, personal digital assistants and navigations, display units such as organic light emitting diodes, polymer light emitting diodes, and polarizers, coatings, adhesives, and adhesives. used

The release film protects the surface of an adherend such as an adhesive, acts as a carrier of an adherend, or serves as a coating substrate. It can be removed at the time of manufacture or when necessary.

Such a release film is mainly composed of a release layer obtained by applying a silicone-based release agent composition containing a silicone-based release resin and a crosslinking agent on a film base layer such as PET, PP, or PE and then curing the release layer.

In the case of manufacturing by coating an adherend on a release film, the release layer of the release film should have good wettability to the adherend, and should have adequate adhesiveness to the extent that the adherend does not spontaneously peel off for a long period of time after manufacture.

For example, when the polyimide film layer is formed on the release film, the polyimide coating liquid is well wetted on the release layer, and the polyimide layer formed after the curing process maintains adhesiveness to the release film, so that the polyimide film layer is adhered to the release film during the process. It is necessary to reduce the situation in which the mid layer is peeled off in advance.

Accordingly, a first object of the present invention is to provide a silicone-based release agent composition capable of forming a release layer capable of maintaining appropriate peeling force and having good wettability to an adherend when coating an adherend on a silicone-based release layer.

A second object of the present invention is to provide a silicone-based release film having the above-described characteristics.

In order to solve the above technical problem, the present invention provides a silicone-based release agent composition further comprising a compound represented by the following formula (1) as a silicone-based release agent composition containing a silicone-based release resin and a crosslinking agent.

In Formula 1,

R is a polymerization unit made of an acrylic monomer,

R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group;

x is an integer from 1 to 1,000;

y is an integer from 1 to 1,000.

In the silicone-based release agent composition of the present invention, R may include at least one selected from the group consisting of polymerized units of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate monomers, but is not limited thereto. In particular, it is preferable that R includes at least a polymerization unit made of isobornyl acrylate and other acrylic monomers, wherein the content of isobornyl acrylate is 5 to 30 mol% based on the total number of moles of acrylic monomers. it is more preferable On the other hand, it is preferable that R ₁ and R ₂ are independently of each other particularly hydrogen or a methyl group.

In the silicone-based mold release agent composition of the present invention, R preferably includes a polymerization unit composed of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate, wherein the acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate The content of the rate is preferably 10 to 40 mol%, 20 to 60 mol%, and 5 to 30 mol%, respectively, based on the total number of moles of acrylic groups.

In the silicone-based release agent composition of the present invention, the compound of Formula 1, R includes a polymerized unit of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate, x is an integer from 100 to 1,000, and y is 100 It is more preferably an integer of 1 to 1,000.

In the silicone-based release agent composition of the present invention, the content of the compound represented by Formula 1 may be 0.1 to 30 parts by weight based on 100 parts by weight of the silicone-based release resin.

The present invention provides a release film comprising a base layer and a release layer laminated on at least one surface of the base layer and made of a cured product of the silicone-based release agent composition described above. Such a release film may be manufactured in a form in which polyimide layers are laminated by coating a polyimide coating solution.

According to the present invention, by adding the compound represented by Formula 1 to a silicone-based release agent composition containing a silicone-based release resin and a crosslinking agent, the release layer formed therefrom has good wettability to the adherend when coating the adherend, and thus uniformly adheres the adherend. can be manufactured In addition, an appropriate peeling force is maintained with respect to the adherend, and the processability is good.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The silicone-based release agent composition comprising the silicone-based release resin and a crosslinking agent of the present invention further includes a compound represented by Formula 1 below.

<Formula 1>

In Formula 1,

R is a polymerization unit made of an acrylic monomer,

R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group;

x is an integer from 1 to 1,000;

y is an integer from 1 to 1,000.

As described above, in the case of manufacturing by coating an adherend on a release film, the release layer of the release film should have good wettability to the adherend, and should have appropriate adhesiveness to the extent that the adherend does not spontaneously peel off for a long period of time after manufacture. do. For example, when a polyimide film layer is formed on a release layer cured with a conventional silicone-based release agent composition containing a silicone-based release resin and a crosslinking agent, the polyimide coating liquid does not wet the release layer well, and the polyimide coating liquid does not wet well on the release layer. The polyimide layer formed after the curing process of the coating liquid is easily peeled off from the release layer, resulting in a decrease in fairness.

According to the present invention, the aforementioned problems can be improved by adjusting the surface energy of the release layer by adding the compound of Formula 1 to the silicone-based release agent composition.

In the silicone-based release agent composition of the present invention, R may include at least one selected from the group consisting of polymerized units of acrylic acid, 2-ethylhexyl acrylate, and isobornyl acrylate monomers. In particular, R preferably includes at least a polymerization unit composed of isobornyl acrylate and other acrylic monomers, and in this case, the content of isobornyl acrylate is more preferably 5 to 30 mol% based on the total number of moles of acrylic groups. . Isobornyl acrylate has an effect of improving adhesion to the substrate layer in particular.

In the silicone-based release agent composition of the present invention, the R preferably includes a polymerized unit of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate, in terms of achieving the desired effect in a balanced manner, acrylic acid, 2 - The content of ethylhexyl acrylate and isobornyl acrylate polymerization units is more preferably 10 to 40 mol%, 20 to 60 mol%, and 5 to 30 mol%, respectively, based on the total number of moles of acrylic groups. Due to the acrylic acid polymerization unit, there is an effect of appropriately imparting adhesiveness in addition to release property, and there is an effect of improving wetting property due to 2-ethylhexyl acrylate.

In the silicone-based release agent composition of the present invention, R of the compound of Formula 1 includes acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate polymer units, x is an integer from 100 to 1,000, and y is from 100 to 1,000 An integer is most preferred.

In the silicone-based release agent composition of the present invention, the content of the compound represented by Formula 1 may be 0.1 to 30 parts by weight based on 100 parts by weight of the silicone-based release resin in consideration of the wetting property and peeling property of the adherend, and more preferably 1 to 25 parts by weight, more preferably 3 to 20 parts by weight, particularly preferably 4 to 6 parts by weight.

In the silicone-based release agent composition of the present invention, as the silicone-based release resin, any silicone-based release resin capable of imparting release properties to a release film may be used without particular limitation. For example, addition reaction type or condensation reaction type thermosetting silicone resin can be used, and polydimethylsiloxane (PDMS) can be exemplified as a representative. In PDMS, the vinyl group of SiCH=CH2 participates in the curing reaction to improve the durability of the release layer, and a release film having necessary peel strength can be prepared according to the content of the compound of Formula 1 and the crosslinking agent.

In the silicone-based release agent composition of the present invention, the crosslinking agent may include at least one of an epoxy-based crosslinking agent, a silicone-based crosslinking agent, a urethane-based crosslinking agent, an acrylic-based crosslinking agent, and an amide-based crosslinking agent, but is not limited thereto. Representatively, hydrogensilane, which is a silicone-based crosslinking agent, may be exemplified.

The content of the crosslinking agent may be 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the silicone compound. By adding a crosslinking agent to the composition for the release layer, it is possible to effectively suppress an increase in the release peel force of the release film according to the release rate. In addition, it is possible to improve the durability of the release film containing the cured product of the composition for the release layer.

In addition, the silicone-based release agent composition of the present invention may include a curing agent. The curing agent may include at least one of a tin-based curing agent, a platinum-based curing agent, a cerium-based curing agent, and a titanium curing agent. As the curing agent is included, the silicone-based release agent composition can be cured more stably. The content of the curing agent may be 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the silicone-based release resin.

In addition, the silicone-based release agent composition of the present invention may contain an organic solvent. The organic solvent may include at least one of methyl ethyl ketone, toluene, ethyl acetate, hexane, and heptane, but is not limited thereto. The content of the organic solvent may be, for example, 200 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the silicone compound so that the composition has an appropriate viscosity suitable for coating.

In addition, it will be taken for granted that the silicone-based release agent composition of the present invention may further include other known additives such as a release agent, a silane coupling agent, an initiator, and silica particles, if necessary.

The above-described silicone-based release agent composition may be formed as a release layer by applying the above-described silicone-based release agent composition on top of a base layer made of polyester such as polyethylene terephthalate (PET), polyethylene, polypropylene, or the like, and thermally curing the release agent composition. As a method of applying the composition, a known method such as a bar coat method, a doctor blade method, a reverse roll coat method, or a gravure roll coat method can be used.

The release film having the release layer of the present invention laminated on the substrate layer may be manufactured as a release film having a polyimide layer laminated on the release layer by, for example, coating and curing a polyimide coating solution on the release layer. Not limited.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<Evaluation of release peel force>

The release layer of the release film was attached to Tesa7475 standard adhesive tape by reciprocating compression 3 times with a load of 2Kg, stored at 25 ℃ and 50 RH% atmosphere for 24 hours or 72 hours, respectively, and then measured at 25 ℃ and 50 RH% atmosphere. (AR-1000, Chem Instruments Co.) was used to measure the release peel force. For a sample size of 50 Х1,500 ㎜ and a peel force measurement of 250 Х 1,500 ㎜, it was performed at a speed of 0.3 m/min under a 180° peel angle, and the average value of 5 repeated measurements was obtained. ) was obtained.

<Evaluation of release peel force change rate>

It was calculated as the change rate of the release peel force after 1 day of storage for the release peel force after 7 days of storage.

<Surface energy evaluation>

The contact angle was measured by dropping ultrapure water and diiodomethane on the release film using a contact angle analyzer tester, and the measured contact angle was entered into the Owens-wendt equation to determine the surface energy [Total=Dis(dispersive term)+ Pol (polar term)].

'Pol' means the surface energy that represents the polar tendency calculated by dropping ultrapure water on the release film, and 'Dis' means the surface energy that represents the non-polar tendency that is calculated by dropping diiodomethane. The total surface energy corresponds to the sum of the surface energies (Pol and Dis).

<Evaluation of glass adhesion peel force>

The release layer was cut to a size of 1*1 inch, laminated on soda lime glass, and then attached by lamination by reciprocating three times using a 2 kg roller. Then, after storage for 1 day, the peel force was measured.

<Evaluation of processability of polyimide>

1) Evaluation of wettability

After laminating the polyimide film on the release layer and reciprocating three times using a 2 kg roller, if it adheres well after 10 minutes, ◎ (Excellent), if it falls off after 5 minutes, ○ (Good), after 1 minute If it fell, it was evaluated as △ (Poor), and if it fell immediately after lamination, it was evaluated as X (NG).

2) Evaluation of peeling characteristics

A polyimide film is laminated on the release layer, reciprocated three times using a 2 kg roller, then cut to have a width of 1 inch and a length of 20 mm, and then the release characteristics of the interface between the release layer and the polyimide film are evaluated. did X (NG) when the release film and the polyimide film are firmly bonded during peeling and are not separated, △ (Poor) when the interface is lifted by movement or transportation before peeling, △ (Poor) when the interface between the release film and the polyimide film is not lifted ○ (Good), the interface between the release film and the polyimide film is not separated to the extent that it is lifted with the fingertips, and external force is applied by bending the laminated film The case of being easily separated was qualitatively evaluated as ◎ (Excellent).

Example 1 to 4

A silicone-based release agent composition was prepared according to the components and content ratios shown in Table 1 below.

A release silicone resin was added to an organic solvent (Tol: toluene, EAC: ethyl acetate, MEK: methyl ethyl ketone) and stirred. After adding and stirring the compound of Formula 1 thereto, a platinum-based curing agent was added and stirred to prepare a silicone-based release agent composition.

The silicone-based release agent compositions of Examples 1 to 4 according to Table 1 were coated on an untreated PET film (SKC SGO0) using Mayer bar No. 8, followed by thermal curing at 130 ° C. for 1 minute, followed by curing at 50 ° C. for 24 After aging for a period of time, release films each having a thickness of 75 μm were prepared.

Subsequently, N-methylpyrrolidone varnish of polyimide (Dongbaek Fine Chem, DFPI-101) was coated on each of the prepared release films and then thermally cured to form a polyimide layer having a thickness of 5 μm.

Surface energy and the like were evaluated and listed in Table 1 below.

Meanwhile, the release silicone resin, the crosslinking agent, and the compound of Formula 1 used in Table 1 are as follows.

Releasable silicone resin: Shin-Etsu's KS-847H

Crosslinking agent: X-92-122 of Shin-Etsu Co., Ltd.

The compound of Formula 1: 2-ethylhexyl acrylate, acrylic acid, isobornyl acrylate and MAI of the following formula were dissolved in 151.94 mmol, 90.20 mmol, 60.01 mmol and 0.03 mmol, respectively, in ethyl acetate, and then reacted at 80° C. for 6 hours. To prepare the compound of Formula 1.

(Wako Pure Chemical Industries, VPS-1001, 수평균 분자량 80,000~120,000 g/mol), "~~~Si~~~" 부분은 Si-Si 결합이 반복되는 것을 의미한다.Macro Azo Initiators (MAIs):

(Wako Pure Chemical Industries, VPS-1001, number average molecular weight 80,000 to 120,000 g/mol), "~~~Si~~~" means repeated Si-Si bonds.

comparative example 1 to 6

A release agent composition according to Table 1 (Comparative Example 1) and a commercially available release film (Comparative Example 2-6) were used.

Formulation (wt%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 solvent
(Tol:EAC:MEK)
(40:40:20) 100 100 100 100 100 untreated
PET Film
(CE900
Kolon) urethane
Primer treated release film (U483,
Toray) acryl
Primer treated release film (XG545B
TAK) interface
Activator treated release film (XD536N, TAK) silicon
Release film (RF02N, SKC HT&M) release silicone resin
(KS-847H, Shin-Etsu) 5 5 5 5 5 cross-linking agent
(X-92-122, Shin-Etsu) 0.1 0.1 0.1 0.1 0.1 Platinum based curing agent (PL-50T) 0.25 0.25 0.25 0.25 0.25 Compound of Formula 1 0.15 0.25 0.5 One 0 PI
Machining result Wetting Castle ○ ◎ ◎ ◎ X ◎ ○ ○ ○ X peeling properties ○ ◎ ○ ○ X X X X △ X Glass adhesion peel force (gf/in) 0.2 2.7 6.1 13.1 17.7 unattached unattached unattached unattached unattached variant
Peel force
(gf/in) 70℃ (1 day) 123.5 314.0 1021.4 1256.7 12.3 1785.6 1456.1 1555.0 897.1 13.4 70℃ (7 days) 431.1 999.3 1943.1 2751.8 17.1 2561.4 2011.3 1985.4 1765.1 16.5 Change rate (%) 249% 218% 90% 119% 39% 43% 38% 28% 97% 23% surface
energy
(mN/m) Dis 26.51 31.19 34.93 36.07 21.54 43.18 34.51 31.55 27.03 22.10 Pol 0.78 0.81 0.99 0.91 0.43 8.44 2.43 3.81 0.41 0.50 Total 27.29 32.00 35.92 36.98 21.97 51.62 36.94 35.36 27.44 22.60

Referring to the results of Table 1, it can be seen that when the release layer formed using the release agent compositions of the embodiments according to the present invention is coated on the adherend, the wettability to the adherend is good and an appropriate peel force can be maintained.

Claims (10)

In the silicone-based release agent composition comprising a silicone-based release resin and a crosslinking agent,
A thermosetting silicone-based release agent composition further comprising a compound represented by Formula 1 below:

In Formula 1,
R is a polymerization unit made of an acrylic monomer,
R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group;
x is an integer from 1 to 1,000;
y is an integer from 1 to 1,000. According to claim 1,
The R is a heat-curable silicone-based release agent composition, characterized in that it comprises at least one selected from the group consisting of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate monomer polymerized units. According to claim 2,
Wherein R is a thermosetting silicone-based release agent composition comprising at least one of a polymer unit of isobornyl acrylate monomer, a polymer unit of acrylic acid monomer and a polymer unit of 2-ethylhexyl acrylate . According to claim 3,
The heat-curable silicone-based release agent composition, characterized in that the content of the polymerized unit of the isobornyl acrylate monomer is 5 to 30 mol% based on the total number of moles of acrylic groups. According to claim 3,
Wherein R is a thermosetting silicone-based release agent composition, characterized in that it comprises a polymerized unit of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate monomers. According to claim 5,
The content of the polymerized units of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate monomers is 10 to 40 mol%, 20 to 60 mol%, and 5 to 30 mol%, respectively, based on the total number of moles of acrylic groups. A thermosetting silicone-based mold release agent composition. According to claim 1,
In the compound of Formula 1, R includes a polymerization unit composed of acrylic acid, 2-ethylhexyl acrylate and isobornyl acrylate monomers, and x and y are each independently an integer of 100 to 1,000. Thermosetting silicone-based release agent, characterized in that composition. According to claim 1,
The content of the compound represented by Formula 1 is 0.1 to 30 parts by weight based on 100 parts by weight of the silicone-based release resin. base layer; and a release layer laminated on at least one surface of the substrate layer and made of a thermally cured material of the silicone-based release agent composition according to any one of claims 1 to 8. The release film according to claim 9, further comprising a polyimide layer laminated on the release layer of the release film.