JP2626816B2 - Release treatment agent - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a releasable treating agent, and more particularly, to a product using an adhesive such as an adhesive tape, an adhesive label, an adhesive sheet, etc. The present invention relates to a release treatment agent that can make the back surface of a base material such as a tape or the like or the surface of a release paper contactable.

(Prior art) Conventionally, as release agents used for the above purpose, polymer compounds such as acrylic acid type, polyester type, polyamide type and the like and organopolysiloxane type compounds having long-chain alkyl groups are known. It is used to form a release surface on the back of an adhesive tape or adhesive sheet or on the surface of release paper. Among these, organopolysiloxane compounds are excellent in properties such as releasability and residual adhesiveness.

(Problems to be Solved by the Invention) Conventional organopolysiloxane-based compounds have the above-mentioned properties, but the release force is not appropriate, and high temperature baking is required at the time of coating on a substrate. There was a problem that the material film could not be used. In addition, some substrates have insufficient adhesiveness to the substrate and cannot be used for various types of substrates.

Also, since the releasable polysiloxane compound has a low critical surface tension, it cannot be written on the release surface, and cissing development often occurs when a pressure-sensitive or heat-sensitive adhesive is applied to the release surface. However, there was a problem that a good coated surface could not be formed.

Accordingly, an object of the present invention is to provide a release treatment agent which can be baked at a low temperature and can be applied to a thermoplastic resin film or the like.

Another object of the present invention is to provide a release treating agent which has no selectivity to a substrate and can form a release surface on any substrate.

Still another object of the present invention is to provide a release treatment agent capable of forming a writable release surface on the surface with an aqueous ink or an oil-based ink.

(Means for Solving the Problems) The above object is achieved by the present invention described below.

That is, the present invention relates to a release treatment agent containing a resin having a siloxane segment and a polyester segment, wherein the resin has an active hydrogen group and a ring-opening copolymer of a siloxane compound and a lactone compound containing no urethane bond. And a siloxane-modified polyester resin containing no urethane bond.

(Function) By using a specific polyester resin having a siloxane segment and a polyester segment, a release surface that can be baked at a low temperature, has no selectivity to a substrate, can be written with a pen or the like, and has an appropriate release property is formed. I can do it.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

The siloxane-modified polyester resin containing no urethane bond used in the present invention is obtained by ring-opening copolymerizing a siloxane compound having an active hydrogen group and containing no urethane bond with a lactone compound.

Preferred examples of the siloxane compound containing an active hydrogen group and containing no urethane bond used in the present invention include the following compounds.

(1) Amino-modified siloxane oil (M = 1 to 10, n = 2 to 10, R = CH ₃ or OCH ₃ ) (M = 1 to 10, n = 2 to 10, R = CH ₃ or OCH ₃ ,
R ′ = aliphatic divalent group or aliphatic ether group) (M = 0 to 200) (N = 2 to 10) (R = lower alkylene group, 1 = 2 to 200, m = 2 to 2
00, n = 2 to 200) (M = 1 to 200, R = lower alkylene group) (2) Epoxy-modified siloxane oil (N = 1 to 200) (M = 1 to 10, n = 2 to 10) (N = 1 to 200) (1 = 2 to 200, m = 2 to 200, n = 2 to 200) (M = 1 to 10) (M = 1 to 10, n = 2 to 10) The above epoxy compound can be used by reacting it with a polyol, polyamine, polycarboxylic acid or the like to have an active hydrogen group at a terminal.

(3) alcohol-modified siloxane oil (N = 1 to 200) (M = 1 to 10, n = 2 to 10, R = aliphatic divalent group or aliphatic ether group) (N = 0 to 200) (1 = 1 to 10, m = 10 to 200, n = 1 to 5) (R = lower alkyl group, R ′ = hydrogen atom, alkyl group,
K = 1 to 250, 1 = 0 to 5, m = 0 to 50, n = 1
To 5) (R = lower alkyl group, k = 1 to 250, 1 = 0 to 5, m = 0 to 50, n = 2 to 5) (4) Mercapto-modified siloxane oil (M = 1 to 10, n = 2 to 10) (N = 2 to 10) (1 = 2 to 200, m = 2 to 200, n = 2 to 200) (M = 1 to 200, R = lower alkylene group) (5) Carboxyl-modified siloxane oil (M = 1 to 10, n = 2 to 10) (N = 1 to 200) (1 = 2 to 200, m = 2 to 200, n = 2 to 200) (N = 1 to 200, R = lower alkylene group) The siloxane compound having an active hydrogen group as described above and containing no urethane bond is an example of a preferred siloxane compound in the present invention. However, the compounds exemplified above and other siloxane compounds are currently commercially available and can be easily obtained from the market, and all of them can be used in the present invention.

In the present invention, a lactone compound having an active hydrogen group and reacting with a siloxane compound containing no urethane bond is a lactone capable of forming a polyester by conventional lactone ring-opening polymerization, such as ε-caprolactone and δ-valerolactone. Compounds, these alkyls,
Mono- or di-substituted derivatives such as halogen, haloalkyl, alkoxy and alkoxyalkyl can be used as well. Particularly preferred lactone compounds are ε-caprolactone and derivatives thereof.

The reaction between the siloxane compound and the lactone compound is carried out by mixing the two, preferably using an appropriate catalyst under a nitrogen stream, and reacting at a temperature of 150 to 200 ° C. for several hours to several tens of hours, A siloxane-modified polyester copolymer having a desired siloxane segment and polyester segment is obtained.

Both can be reacted at any reaction ratio, but for the purpose of the present invention, it is preferable to react at a ratio such that the siloxane segment accounts for 10 to 80% by weight in the obtained copolymer. . When the amount of the siloxane compound used is too small, the releasability and blocking resistance of the finally obtained siloxane-modified polyester-based resin become insufficient. On the other hand, when the amount is too large, the film-forming properties of the obtained siloxane-modified polyester-based resin and This is not preferable because the strength of the coating film decreases.

Although the polyester resin as described above has excellent release properties and blocking resistance, it is easily soluble in various organic solvents and can form an excellent flexible release layer.

However, the above copolymer contains the unreactive siloxane compound contained in the siloxane compound used as it is and varies depending on the siloxane compound used and the copolymerization ratio. 1.0 to 1
Since it is contained as an impurity at a ratio of 0% by weight,
It is preferable to remove these impurities. Although the object of the present invention can be achieved even if these impurities are present, these impurities may bleed out to the surface of the coating film after the release layer is formed, and may cause a problem. However, since the impurities are non-reactive, they do not react with the crosslinking agent, and the problem of bleed-out is not solved even with a crosslinked film.

Such impurities are difficult to separate at the raw material stage,
In the present invention, after the copolymerization, continuously or after about
It can be easily removed by a reduced pressure treatment at a temperature of 100 to 250 ° C., preferably 10 mmHg, preferably 5 mmHg or less under an inert atmosphere such as nitrogen gas, and contains a substantially unreacted siloxane compound. Polyester resin is obtained. In the present invention, substantially not containing
It refers to those having an unreacted siloxane compound content of less than 1.0%.

The polyester resin used in the present invention as described above may be of any molecular weight, but in consideration of usability, about 1,00
The molecular weight is preferably about 0 to 30,000, and the molecular weight may be adjusted by using a known technique as it is. Further, the polyester resin has a reactive hydroxyl group at a terminal, and can be cross-linked (cured) by various cross-linking agents (curing agents).

The release treatment agent of the present invention is obtained by dissolving the polyester resin in a suitable organic solvent, for example, at a concentration of 5 to 30% by weight, and in addition to release properties, lubricity, and blocking resistance, A release layer having excellent migration resistance and bleeding resistance can be formed.

Preferred as such organic solvents are methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate and the like, and acetone , Cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, and the like.

Further, when forming the release layer, it is possible to form a crosslinked release layer having more excellent physical properties by crosslinking with various crosslinking agents.

As the cross-linking agent, any compound containing two or more functional groups capable of reacting with the terminal hydroxyl group of the polyester resin, for example, a polyisocyanate compound or a polyepoxy compound can be used. Further, the terminal hydroxyl group can be replaced with another functional group. If modified, it can be crosslinked with a crosslinking agent having a hydroxyl group, an amino group, an aldehyde group, or the like. Particularly preferred crosslinking agents are polyisocyanate compounds.

As the polyisocyanate, any known polyisocyanate can be used. For example, preferred are 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, and 1 , 4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and the like. Of course, urethane prepolymers obtained by reacting a polyol or polyamine having a molecular weight with a terminal isocyanate can also be used.

The release layer crosslinked with the crosslinking agent as described above becomes a tough release layer which is excellent not only in releasability, lubricity and blocking resistance but also in migration resistance and bleeding resistance.

The above-mentioned polyester resin solution is a release treating agent used in the present invention by itself, and can be used as it is, and further various known additives such as coloring agents, cross-linking agents, stabilizers, and fillers. Additives can be optionally added.

In particular, conventionally known mold releasing substances as one kind of additives, for example, wood powder, talc, silica, boron nitride, alumina, polyethylene resin powder, benzoguanamine resin powder, silicone resin powder, melamine resin powder, fluororesin powder,
Phenol resin powder and the like can be added in the range of 0 and 200 parts by weight per 100 parts by weight of the polyester resin. Further, a general thermoplastic or thermosetting resin can be used in combination as an additive.

(Effects) According to the present invention as described above, by using a polyester resin having a siloxane segment and containing no urethane bond, low-temperature baking is possible, there is no selectivity to a base material, and it is possible to write with a pen or the like and to be moderate. A peelable surface having peelability can be formed.

(Examples) Next, the present invention will be described more specifically with reference to reference examples, examples, and comparative examples. In the following description, parts and percentages are by weight unless otherwise specified.

Reference Example 1 (M and n are values at which the amine equivalent becomes 3,800) In a reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser, 240 parts of ε-caprolactone and the above structure (1) are provided. 100 parts of an amino-modified siloxane oil and 0.05 part of tetrabutyl titanate were charged and reacted at 180 ° C. for 10 hours in a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction, and the non-reactive siloxane compound and unreacted substances contained in the raw material siloxane compound were completely removed. 15 unreacted siloxane compounds removed
Department. The resulting product is a waxy polysiloxane-polyester copolymer having a hydroxyl value of 16 and a melting point of 72 ° C.
The copolymer was dissolved in methyl ethyl ketone to obtain a 30% solution.

Reference example 2 (M and n are values at which the amine equivalent becomes 3,500) In the same manner as in Reference Example 1, 160 parts of ε-caprolactone,
140 parts of amino-modified siloxane oil having the above structure (2) and 0.04 part of tetrabutyl titanate are charged,
The reaction was performed at a temperature of 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction, and the non-reactive siloxane compound and unreacted substances contained in the raw material siloxane compound were completely removed. 18 unreacted siloxane compounds removed
Department. The resulting product is a waxy polysiloxane-polyester copolymer having a hydroxyl value of 18 and a melting point of 76 ° C.
The copolymer was dissolved in methyl ethyl ketone to obtain a 30% solution.

Reference Example 3 (M and n are values at which the hydroxyl value becomes 25) In the same manner as in Reference Example 1, 200 parts of ε-caprolactone,
160 parts of alcohol-modified siloxane oil having the above structure (3) and 0.05 part of tetrabutyl titanate were charged and reacted at 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 4 mmHg for 1 hour to complete the reaction, and the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound were completely removed. 18 unreacted siloxane compounds removed
Department. The resulting product is a waxy polysiloxane-polyester copolymer having a hydroxyl value of 12 and a melting point of 78 ° C.
The copolymer was dissolved in methyl ethyl ketone to obtain a 30% solution.

Reference example 4 (M and n are values at which the hydroxyl value becomes 32) In the same manner as in Reference Example 1, 180 parts of ε-caprolactone,
160 parts of alcohol-modified siloxane oil having the above structure (4) and 0.04 part of tetrabutyl titanate were charged and reacted at 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 3 mmHg for 1 hour to complete the reaction and completely remove the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound. 16 unreacted siloxane compounds removed
Department. The resulting product is a waxy polysiloxane-polyester copolymer having a hydroxyl value of 14 and a melting point of 75 ° C.
The copolymer was dissolved in methyl ethyl ketone to obtain a 30% solution.

Examples 1 to 4 and Comparative Examples 1 and 2 The following release agents of the present invention and comparative examples were coated on one surface of a polyvinyl chloride film having a 100% modulus of 60 kg / cm ² and a thickness of 50 μm with a solid content of 0.6 g / m ^2. Was uniformly applied so as to have a coating amount of, and dried by heating at 80 ° C for 30 seconds to prepare a sample having a peelable coating layer. When the temperature was raised to a high temperature (100 ° C. or higher), the polyvinyl chloride film was softened, and the shape as the film could not be maintained.

Acrylic adhesive tape (manufactured by Sekisui Chemical) having a width of 20 mm was pressed on the coated base material thus prepared with a rubber roller having a weight of 2 kg, and after one day at normal temperature (20 ° C., 52% humidity) and at a high temperature (40 ° C.,
After leaving for 3 days at a humidity of 90% or more), the peelability, residual adhesive strength, residual adhesive strength retention, detachability of the peelable coating layer, and writability with magic ink were measured, and the results are shown in Table 1 below. .

Example 1 100 parts of the resin solution of Reference Example 1 Coronate L (adduct of trimethylolpropane and TDI) 2 parts 250 parts of methyl ethyl ketone Example 2 100 parts of the resin solution of Reference Example 2 Fluororesin powder (Daikin Industries; Lubron L-2) 5 parts Coronate L 2 parts Methyl ethyl ketone 250 parts Example 3 100 parts resin solution of Reference Example 3 Coronate L 2 parts Methyl ethyl ketone 250 parts Example 4 Resin solution of Reference Example 100 100 parts Coronate L 2 parts Silicone resin powder (Toshiba Silicone, Tospearl 12
0) 5 parts Methyl ethyl ketone 250 parts Comparative Example 1 Compound of structural formula (1) of Reference Example 1 100 parts Coronate L 2 parts Methyl ethyl ketone 250 parts Comparative Example 2 Silicone resin (KS-841, manufactured by Shin-Etsu Chemical) 100 parts Catalyst (PL- 7) 1 part Toluene 1,000 parts Each evaluation was performed as follows.

Peelability: Adhesive tape with a width of 20 mm is applied to the peelable coating layer, and stored at 40 ° C under a load of 20 g / cm ² for 24 hours.
The force (g) required for pulling at an angle of 180 ° at a speed of mm / min and peeling was measured (20 ° C).

Residual adhesive strength: The adhesive tape after the peelability measurement was applied to a stainless steel plate # 280, reciprocated once over a 2 kg tape roller, and after 30 minutes, pulled at a speed of 300 mm / min at an angle of 180 ° and peeled. The required force (g) was measured (20 ° C.).

Residual adhesive strength retention: Percentage of residual adhesive strength when a clean adhesive tape that was not subjected to peel resistance was attached to a stainless steel plate # 280 and the adhesive strength (320 g / 20 mm) to the stainless steel plate was 100%. ing.

Drop-off property: A drop-off test of the strippable coating layer is performed on the material after the gauze is reciprocated once with a load of 50 g / cm ^{2 on} the strippable coating layer.

Writability with magic ink: Characters were written on the peelable coating layer with a commercially available oil-based magic ink, and the presence or absence of repelling of the ink during writing was examined.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Iwao Mihozu 2-5-2 Fujimi, Ageo City, Saitama Prefecture (72) Inventor Masafumi Saito 4-18-13 Ukima, Kita-ku, Tokyo (72) Inventor Katsumi Kuriyama Saitama 1135-1 Kuri Shimoma, Koshigaya, Japan (56) References JP-A-1-126389 (JP, A) JP-A-2-113015 (JP, A)

Claims (5)

(57) [Claims] 1. A releasable treating agent containing a resin having a siloxane segment and a polyester segment,
A release treating agent, wherein the resin is an siloxane-modified polyester resin containing no urethane bond, which is a ring copolymer of a siloxane compound and a lactone compound containing an active hydrogen group and containing no urethane bond. 2. The release treating agent according to claim 1, wherein the siloxane segment accounts for 10 to 80% by weight of the siloxane-modified polyester resin. 3. The release treating agent according to claim 1, wherein the siloxane-modified polyester resin contains substantially no unreacted siloxane compound. 4. The release treatment agent according to claim 1, further comprising a release substance. 5. The release treating agent according to claim 1, which is an organic solvent solution.