JP2002155136A - Cation curable composition containing oxetane compound as principal component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cation curable composition which is a non-silicone type and has an excellent releasability. SOLUTION: The cation curable composition comprises an oxetane compound having a solubility parameter of 7.7-8.3, a light or a heat initiator, and according to demand, a cation curable compound other than the oxetane compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cationically curable composition containing an oxetane compound as a main component. More specifically, the present invention relates to a cationically curable composition having excellent cationic curability and excellent release properties of the obtained cured product.

[0002]

2. Description of the Related Art Release agents are used in large quantities for applications such as separators of acrylic or rubber-based pressure-sensitive adhesives, and silicone-based resins and stearyl group-containing resins are generally used as release agents. As a method of using a release agent, a method of coating a solvent or an emulsion solution or dispersion containing these resins on a film or paper as a base material, followed by drying and heat curing is generally used. However, recently, there has been an increasing movement to eliminate VOC components such as organic solvents from the manufacturing process due to environmental problems.
From the viewpoint of space saving and productivity, active energy rays such as ultraviolet rays and thermosetting resins which do not require an organic solvent are attracting attention instead of conventional solvent-containing resins. On the other hand, as an active energy ray-curable release agent, a cationically-curable silicone release agent in which an epoxy group is introduced into silicone has been developed, but the silicone-based release agent has an excellent release effect. On the other hand, there is a problem of migration of silicone components and contamination of equipment, so that it is difficult to use in applications such as electronic materials. Therefore, it is non-silicone,
In addition, a compound which exhibits a releasing effect comparable to that of a silicone resin and which can be cured by an active energy ray or heat which does not require an organic solvent is widely used industrially as an excellent releasing agent.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cationically curable composition which is non-silicone and has excellent release properties.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, when an oxetane compound having a specific solubility parameter was applied to a release agent, the cured product was excellent. They have found that they have mold release properties, and have completed the present invention. That is, the present invention is a cationically curable composition comprising an oxetane compound having a solubility parameter in the range of 7.7 to 8.3, a light or thermal cationic initiator, and optionally a cationically curable compound other than the oxetane compound.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Solubility parameter (δ) The solubility parameter in the present invention is the molecular attraction constants proposed by Small et al.
This is a calculated value obtained by using F and calculating by the following equation. δ = ΣF / V where δ: solubility parameter, F: molecular attraction constant,
V: Indicates molecular volume. In the present invention, the molecular volume V of the functional group and the molecular attractive constant F are as shown in Table 1 below.
The value obtained for eman was used.

[0006]

[Table 1]

[0007] 2. Oxetane compound (A) The oxetane compound in the present invention is an oxetane compound having a solubility parameter in the range of 7.7 to 8.3,
A compound represented by the following formula (1) having one oxetane ring in the molecule is preferably used.

[0008]

Embedded image (In the formula, X represents a linear or branched alkyl group having 1 to 4 carbon atoms, and Y represents a linear, branched or alicyclic alkyl group having 4 to 22 carbon atoms.)

In the above formula (1), X is preferably a methyl group or an ethyl group, and Y is a group having 6 to 18 carbon atoms.
Is preferably a linear, branched or alicyclic alkyl group.
Particularly preferred X is an ethyl group, and particularly preferred Y is a linear or branched alkyl group having 8 to 18 carbon atoms. Y
Is a branched structure, so that the solubility parameter decreases.
It is extremely effective in expressing releasability. Specific examples of preferred oxetane compounds include 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (heptyloxymethyl) oxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane 3-ethyl-3-
(Octyloxymethyl) oxetane, 3-ethyl-3
Various 3- such as-(dodecyloxymethyl) oxetane
Ethyl-3- (alkoxymethyl) oxetane and the like. Among them, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane is commercially available as Alonoxetane OXT-212 (trade name) manufactured by Toagosei Co., Ltd.

[0010] 3. Light or Thermal Cationic Initiator (B) The light or thermal cationic initiator in the present invention is a polymerization initiator of the oxetane compound, and the photocationic polymerization initiator is a compound that is cleaved by the action of active energy rays to release a strong acid. The thermal cationic polymerization initiator is a compound which is cleaved by the action of heat, that is, an increase in temperature, and releases a strong acid. Examples of the photocationic initiator include UV / E
Compounds described in 3.1.5, pages 63-65 of B-curing material [CMC Co., Ltd., issued in 1992], among which are represented by the following formula (2). A triarylsulfonium hexafluorophosphate salt, a triarylsulfonium hexafluoroantimonate salt in which a phosphorus atom is substituted with an antimony atom, and a diaryliodonium salt represented by a compound represented by the following formula (3) are preferably used.

[0011]

Embedded image

[0012]

Embedded image

Examples of the thermal cation initiator include, for example, Sb
An onium salt of nitrogen, sulfur, phosphorus or iodine having F ₆ , —SbF ₄ , —AsF ₆ , —PF ₆ — or the like as an anion component can be used. Specifically, there are quaternary ammonium salt-type compounds, sulfonium salt-type compounds, phosphonium salt-type compounds, iodonium salt-type compounds, etc., and Adeka Opton CP-66 and CP-77 (trade names, manufactured by Asahi Denka Kogyo KK) ), Sun-Aid SI- manufactured by Sanshin Chemical Industry Co., Ltd.
Commercial products such as 60L, SI-80L, and SI-100L (all of which are trade names) can be used.

4. Other Cationic Curable Compound (C) The cationic curable compound other than the oxetane compound (A) in the present invention is a component that is not an essential component but is preferably used according to the purpose. For example, an epoxy compound and ( Oxetane compounds other than A) are mentioned. As the epoxy compound, a known alicyclic epoxy compound or aromatic epoxy compound having at least one epoxy group in a molecule can be used, and a polyfunctional epoxy compound having two or more epoxy groups is preferable.
Examples of preferred alicyclic epoxy compounds include 3,4-
Compounds having two or more epoxidized cyclohexyl groups, such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate, may be mentioned. These compounds are manufactured by Union Carbide Co., USA
A commercially available RE resin can be used. Specific examples of the aromatic epoxy compound include bisphenol A diglycidyl ether, diglycidyl ether condensate of bisphenol A, and epichlorohydrin modified novolak resin and cresol resin. These epoxy compounds, depending on the performance required for the cured product,
They can be used alone or as a mixture.

As the oxetane compound other than (A), any compound having one or more oxetane rings in the molecule can be used without any particular limitation. Specifically, among various oxetane compounds described in JP-A-8-85775 and JP-A-8-134405,
Oxetane compounds other than the above (A) are exemplified, and among these, compounds having one or two oxetanyl groups are preferable. Examples of the monofunctional oxetane include 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (chloromethyl) oxetane, and the like.
Examples of bifunctional oxetanes include 1,4-bis [(3-
Ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether and the like. These compounds are manufactured by Toagosei Co., Ltd. Aron oxetane OXT-101, OX
It is available as a commercial product such as T-121, OXT-211 and OXT-221 (all are trade names). Further, the oxetane compounds other than (A) used in the present invention include the following because they can increase the crosslink density of the cured product.
Polyfunctional oxetanes higher than functional oxetanes are preferably used.

5. Blending of cationically curable composition The cationically curable composition in the present invention is preferably composed of (A) to (C) described above, and the solubility parameter of the composition is 8.35 or less. Is preferred, and more preferably 8.3 or less. The preferred weight ratio of each component is (A) 75 to 99% by mass,
(B) is 0.1 to 10% by mass, and (C) is 1 to 24%.
% By mass. More preferable mass ratio is that (A) is 80%.
-96 mass%, (B) is 0.2-5 mass%, and (C) is 4-20 mass%. If (A) is less than 75% by mass, the releasability of the cured coating film is poor, and if it exceeds 99% by mass, the curability is reduced. If (B) is less than 0.1% by mass, the curability is low, and if it exceeds 10% by mass, the coating strength of the cured product decreases. If the content of (C) is less than 4% by mass, the curability is insufficient and 2
If it exceeds 5% by mass, the releasability of the cured coating film decreases.

The cationically curable composition further contains additives such as a filler, a coupling agent, a flame retardant, a plasticizer, a low-shrinkage agent, a lubricant, a surface modifier, and a dye / pigment as required. be able to. For the purpose of adjusting the strength of the coating film, modifying the interface / surface, adjusting the viscosity, etc., various resin components such as acrylic resins can be mixed.

[0018]

The present invention will be described more specifically below with reference to examples and comparative examples. All parts of the components in each example are parts by mass. Examples 1-4 and Comparative Example Preparation and Curing of UV Curable Composition After blending the UV curable composition having the composition shown in Table 2 below, a bar coater # was placed on a 50 μm thick PET film.
After forming a coating film using No. 3, it was cured by irradiating ultraviolet rays. Using a conveyor type ultraviolet irradiation device (lamp height = 10 cm, conveyor speed = 10 m / min) equipped with a high pressure mercury lamp of 80 W / cm, curing was performed through two passes. About 1 hour after the irradiation, the pressure-sensitive adhesive tape was pressed by the method shown below, and the releasability of the coating film was evaluated. The results are shown in Table 2.

Adhesive tape peeling strength: A commercially available acrylic pressure-sensitive adhesive tape (Nitto 31B tape) having a width of 19 mm was adhered to the coating film so as to prevent air bubbles from entering the film, and was strongly pressed several times with a rubber roll. Attach the bonded film to room temperature or 50
After leaving the tape at 1 ° C. for one day, the 180 ° peel strength of the tape was measured using a 5 kg load cell using Tensilon UTM-4L manufactured by Toyo Keiki Co., Ltd. Pulling speed is 300mm
/ Min. The calculation of the solubility parameter in the table is
The above procedure was repeated, but the initiator (CD-1
012) was excluded from the calculation.

[0020]

[Table 2]

In Table 2, 1) to 5) show the following compounds. 1) EHOX: 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, Alonoxetane OXT-212 (trade name) manufactured by Toagosei Co., Ltd. 2) DDOX: 3-ethyl-3- (dodecyloxymethyl) Oxetane 3) UVR-6110: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, alicyclic epoxy compound (trade name) manufactured by Union Carbide 4) DOX: bis {1-ethyl (3- Oxetanyl)] methyl} ether, Aron oxetane OXT-221 (trade name) manufactured by Toagosei Co., Ltd. 5) CD-1012: diaryliodonium hexafluoroantimonate, SarCat C manufactured by Saltomer Co.
D-1012 (product name)

Reference Data The calculated values of the solubility parameters of each compound alone are shown in Table 3 below.

[0023]

[Table 3]

[0024]

The cationically curable composition of the present invention provides a cured coating film having excellent release properties, and the strength of the release properties can be easily adjusted by adjusting the solubility parameter. Further, since the viscosity of the blended liquid is low and the safety is high, the coating productivity is also excellent. Utilizing these features, the cationically curable composition of the present invention can be used for a wide range of applications such as paints and coating materials, optical film and sheet materials, molding materials, and electrical insulating materials.

Claims (3)

[Claims] 1. A cationically curable composition comprising an oxetane compound having a solubility parameter in the range of 7.7 to 8.3, a light or thermal cationic initiator, and optionally a cationically curable compound other than the oxetane compound. 2. The cationically curable composition according to claim 1, which is a composition comprising the following (A) to (C), wherein the solubility parameter of the composition is 8.35 or less. (A) An oxetane compound represented by the following formula (1) and having a solubility parameter in the range of 7.7 to 8.3: 75 to 99.
(B) Light or thermal cation initiator: 0.1 to 10 parts by mass (C) Cationic curable compound other than (A): 1 to 24 parts by mass (In the formula, X represents a linear or branched alkyl group having 1 to 4 carbon atoms, and Y represents a linear, branched or alicyclic alkyl group having 4 to 22 carbon atoms.) 3. A release film obtained by applying the cationically curable composition according to claim 1 on a film and curing the curable composition.