JPH0796668B2 - Method for producing releasable resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a releasable resin, and more specifically to a product using an adhesive such as an adhesive tape, an adhesive label, an adhesive sheet, etc. The present invention relates to a method for producing a releasable resin capable of making the back surface of a substrate such as a tape or the like and the surface of a release paper which are in contact with each other have a releasability.

(Prior Art) Conventionally, as peeling treatment agents used for the above-mentioned purpose, polymer compounds such as acrylic acid-based, polyester-based, polyamide, etc. having a long-chain alkyl group bonded and organopolysiloxane-based compounds are known. It is used for imparting releasability to the back surface of an adhesive tape or an adhesive sheet or the surface of a release paper to form a release surface. Among these peeling treatment agents, it is known that organopolysiloxane compounds are excellent in characteristics such as peelability and residual adhesiveness.

(Problems to be Solved by the Invention) Conventional organopolysiloxane-based compounds have the above-mentioned characteristics, but the peeling force is not appropriate, and high-temperature baking is required when coating the substrate, There is a problem that it cannot be used for a plastic substrate film. Further, there is a defect that the adhesion to the base material is insufficient depending on the base material and it cannot be used for various kinds of base materials.

Moreover, since the peelable polysiloxane compound has a small critical surface tension, it cannot be written on the peeling surface, and when a pressure-sensitive or heat-sensitive adhesive is applied to the peeling surface,
There is a problem that a cissing phenomenon often occurs and a good coated surface cannot be formed.

Therefore, an object of the present invention is to provide a peelable resin 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 have no selectivity for the substrate,
It is to provide a releasable resin capable of forming a release surface on any base material.

Still another object of the present invention is to provide a releasable resin capable of forming a releasable surface on which a writable aqueous ink or oily ink can be written.

(Means for Solving Problems) The above object is achieved by the present invention described below. That is, the present invention provides a reaction product of a polysiloxane compound having a reactive group and an organic polyisocyanate, which comprises a reaction product having at least one free isocyanate group and a group capable of reacting with the isocyanate group. It is a method for producing a peelable resin, which comprises reacting the resin with the resin.

(Function) A reaction product of a polysiloxane compound having a reactive group and an organic polyisocyanate, the reaction product having at least one free isocyanate group, and a resin having a group capable of reacting with the isocyanate group. By using a releasable resin obtained by reacting with, it is possible to form a release surface which has no selectivity for a base material and can be applied to a thermoplastic resin film or the like. Writable with oil-based ink.

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

The polysiloxane compound having a reactive group used in the present invention has one or more reactive groups in the molecule, for example,
It is a polysiloxane having an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group and the like.

Preferred examples of the polysiloxane compound having a reactive group include the following compounds.

(1) Amino-modified silicone oil (M = 1 to 10, n = 2 to 10, R = CH ₃ or 0CH ₃ ) (M = 1 to 10, n = 2 to 10, R = CH ₃ or 0CH ₃ ) (M = 0 to 200) (N = 2 to 10) (Branch point = 2 to 3, k = 2 to 200, m = 2 to 200,
n = 2 to 200, R = lower alkyl group) (M = 1 to 200, R = lower alkyl group) (2) Epoxy modified silicone oil (N = 1 to 200) (M = 1 to 10, n = 2 to 10) (N = 1 to 200) (Branch point = 2 to 3, k = 2 to 200, m = 2 to 200,
n = 2 to 200, R = lower alkyl group) (N = 1 to 10) (M = 1 to 10, n = 1 to 10) (3) Alcohol-modified silicone oil (N = 1 to 200) (M = 1 to 10, n = 2 to 10) (M = 0 to 50, n = 0 to 200) (P = 1 to 10, m = 10 to 200) 200, n = 1 to 5) (N = 1 to 200, R = lower alkyl group) (4) Mercapto-modified silicone oil (M = 1 to 10, n = 2 to 10) (N = 2 to 10) (Branch point = 2 to 3, k = 2 to 200, m = 2 to 200,
n = 2 to 200, R = lower alkyl group) (M = 1 to 200, R = lower alkyl group) (5) Carboxyl-modified silicone oil (M = 1 to 10, n = 2 to 10) (N = 1 to 200) (Branch point = 2 to 3, k = 2 to 200, m = 2 to 200,
n = 2 to 200, R = lower alkyl group) (M = 1 to 200, R = lower alkyl group) The polykiloxane compound having a reactive group as described above is
It is an illustration of preferred compounds in the present invention, and the present invention is not limited to these exemplifications. The above-exemplified compounds and other compounds are currently commercially available and easily obtained from the market. Obtained, and any of them can be used in the present invention.

In the method of the present invention, a polysiloxane having a reactive group as described above and a polyisocyanate as described below are reacted so that at least one of the isocyanate groups of the polyisocyanate group remains, and a reaction product having an isocyanate group ( Intermediate). For example, a bifunctional polysiloxane compound, a polyfunctional compound, and a polyisocyanate are reacted in an isocyanate group-rich manner.

Next, by reacting the isocyanate of this reaction product with a resin having a group capable of reacting with a group (modification of the resin), a resin having a polysiloxane segment bonded to a side chain is obtained.

Among various resins capable of reacting with an isocyanate group, preferred ones in the present invention are polyurethane resins, polyurea resins, vinyl resins such as resins containing vinyl alcohol such as polyvinyl butyral resin as a monomer component, and acrylics such as acrylic polyol. Resins and the like, and particularly preferable ones are polyurethane resins and / or polyurea resins. A method of manufacturing the same will be described below by using a polyurethane resin as a typical example.

The polyurethane-based resin having a polysiloxane segment as a side chain is preferably one from the reactive polysiloxane compound and the isocyanate compound when or after adjusting the polyurethane-based resin by reacting a polyol, a polyisocyanate and a chain extender. It is obtained by preparing an intermediate having an isocyanate group of 1) and reacting it with a polyurethane resin.

As the polyol for polyurethane, any conventionally known polyol for polyurethane can be used. For example, the terminal group is preferably a hydroxyl group and has a molecular weight of 300.
To 4,000 polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-ε- Examples thereof include caprolactone diol, polyhexamethylene adipate, carbonate polyol polypropylene glycol, and the like, and those containing an appropriate amount of polyoxyethylene chain in the above polyol.

As the organic polyisocyanate, any conventionally known one can be used, but preferred examples include 4,4′-diphenylmethane diisocyanate (MDI), water-added MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1 2,4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, etc. A urethane prepolymer obtained by reacting a polyol or polyamine having a molecular weight so as to form a terminal isocyanate may be used as a matter of course.

As the chain extender, any conventionally known one can be used, but for example, preferred are ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, 1, 2-propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, isophoronediamine, m-xylylenediamine, hydrazine, water and the like.

Polyurethane-based resins containing a polysiloxane segment obtained from a material as described above in a side chain can be used as a peelable resin, but the preferred one is that the polysiloxane segment accounts for about 0.2 to 70% by weight in the resin. When the polysiloxane segment is about 0.2% by weight, the intended purpose of the present invention cannot be achieved sufficiently.
On the other hand, if the amount exceeds 70% by weight, problems such as a decrease in adhesiveness to the substrate may occur, which is not preferable.

The polyurea-based resin and the polyurethaneurea-based resin can be obtained in the same manner by using polyamine in place of all or part of the polyol in the above.

Further, those having a molecular weight of 2 to 500,000 are preferable, and those having a molecular weight of 2 to 250,000 are most preferable.

The polysiloxane segment-containing polyurethane resin as described above can be easily obtained by a conventionally known production method. These polyurethane-based resins may be prepared without a solvent or may be prepared in an organic solvent,
It is advantageous that the release treatment agent can be used as it is for the preparation of the release treatment agent by preparing it in an organic solvent to be prepared.

Preferred as such an organic solvent 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, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate and the like can also be used. Of course, the above organic solvents can be used as a mixed organic solvent.

By preparing a polyurethane resin in such an organic solvent, a polyurethane resin solution having a polysiloxane segment can be obtained, but the solid content thereof is the same or in the range of about 5 to 60% by weight by adding or removing another solvent. Is preferred. The polyurethane resin may be used in the form of a solution or a dispersion liquid in which the resin is partially or entirely deposited (hereinafter simply referred to as a solution).

The polyurethane resin solution described above is a release treatment agent by itself, and can be used as it is, and further various additives, for example, known additives such as colorants, cross-linking agents, stabilizers and fillers can be optionally added. Can be added to.

In particular, a conventionally known release material as a kind of additive, for example, wood powder, talc, silica, boron nitride, alumina, polyethylene resin powder, benzoguanamine resin powder, silicone resin powder, melamine resin powder, fluororesin powder,
Phenolic resin powder or the like may be added in an amount of 0 to 200 parts by weight per 100 parts by weight of the polysiloxane segment-containing resin. Further, as the additive, a general thermoplastic or thermosetting resin can be used together.

The above examples are mainly about the polyurethane resin, but of course the same applies to the above resins other than the polyurethane resin, by introducing a polysiloxane segment as a side chain into the resin and using it as a peelable resin. can do.

(Effects) According to the present invention as described above, a resin having a polysiloxane segment in the side chain is obtained, and by using this resin, low temperature baking is possible, there is no selectivity for the substrate, and writing with a pen or the like is possible. It is possible to form a peeling surface having an appropriate peeling force.

Next, the present invention will be specifically described with reference to examples and evaluation examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on weight.

Example 1 (Production Example of Intermediate) (Production of Intermediate) Addition product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, manufactured by Nippon Polyurethane Co., NCO% = 12.5%, solid) 175 parts of a mold component of 75%) are thoroughly stirred with 500 parts of ethyl acetate at 50 ° C., and 880 parts of terminal aminopropylpolydimethylsiloxane (molecular weight 2,200) having the following structure is gradually added dropwise thereto for reaction.

(N is a value at which the molecular weight is 2,200) After completion of the reaction, ethyl acetate was evaporated to obtain 976 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate groups of 2,270 / cm remains, and
An absorption band due to the -Si-O-C group was shown at 090 / cm.

When the free isocyanate group of this intermediate was quantified, the theoretical value was 0.83%, while the measured value was 0.78%.
Met.

Therefore, the main structure of the above intermediate is estimated by the following formula.

Reference Example 2 300 parts of ethyl acetate and 24 parts of phenylisocyanate were added to 196 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight 980) having the following structure, and the mixture was stirred well at 60 ° C. and reacted to give a transparent liquid reaction product 213 Parts were obtained.

(N is a value at which the molecular weight is 980) Next, an adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Asahi Kasei Co., Ltd., NCO% = 23.
(5%) 52 parts and 100 parts of ethyl acetate are stirred well at 60 ° C., and 220 parts of the above reaction product is gradually added dropwise into the mixture to react them, and 263 parts of a colorless transparent liquid intermediate is obtained. It was

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group at 2,270 / cm remains, and
An absorption band due to the -Si-O-C group was shown at 0 / cm.

Quantifying the free isocyanate groups of this intermediate,
The measured value was 0.78%, while the theoretical value was 1.54%.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

(Modification of resin) 150 parts of polybutylene adipate having a hydroxyl group at the end and a molecular weight of 2,000, 20 parts of 1,3-butylene glycol and 52 parts of tolylene diisocyanate are subjected to an addition reaction with 412 parts of methyl ethyl ketone, and a viscosity of 200 poise / 20 ° C. A polyurethane resin solution (solid content 35%) was obtained.

To 100 parts of this polyurethane solution, 5 parts of the above intermediate was added and reacted at 80 ° C. for 3 hours to obtain a modified resin in which the intermediate and polyurethane were bonded.

In the obtained modified resin, no isocyanate group was found in the infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Example 2 (Production of Intermediate) 600 parts of ethyl acetate and 24 parts of phenylisocyanate were added to 196 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight 980) having the following structure, and the mixture was stirred well at 60 ° C. and reacted to be transparent. 213 parts of a liquid reaction product were obtained.

(N is a value at which the molecular weight is 980) Next, an adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Asahi Kasei Co., Ltd., NCO% = 23.
(5%) 52 parts and 100 parts of ethyl acetate are stirred well at 60 ° C., and 220 parts of the above reaction product is gradually added dropwise into the mixture to react them, and 263 parts of a colorless transparent liquid intermediate is obtained. It was

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group at 2,270 / cm remains, and
An absorption band due to the -Si-O-C group was shown at 0 / cm.

Quantifying the free isocyanate groups of this intermediate,
The theoretical value was 1.54%, while the measured value was 1.37%.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

(Modification of Resin) A modified resin was obtained in the same manner as in Example 1 except that the above intermediate was used. In the obtained modified resin, no isocyanate group was found in the infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Example 3 (Production of Intermediate) 230 parts of terminal aminopropylpolydimethylsiloxane (molecular weight 1,150) having the following structural formula, 600 parts of ethyl acetate and 15 parts of n-butyraldehyde were added, and the reaction was carried out by stirring well at 80 ° C. And remove the generated water outside the system under reduced pressure.
After reacting for a period of time, 238 parts of a transparent liquid reaction product was obtained.

(N is a value at which the molecular weight is 1,150) Next, an adduct of 1 mol of trimethylolpropane and 3 mol of xylylenediisocyanate (Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd., NCO% = 11.5%, solid content 75%) 186 Parts and 300 parts of ethyl acetate were stirred well at room temperature, 490 parts of the above reaction product was gradually added dropwise thereto, and reacted at 60 ° C.

After the reaction was completed, ethyl acetate was evaporated to obtain 610 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate groups of 2,270 / cm remains, and
An absorption band due to the -Si-O-C group was shown at 090 / cm.

Also, when the free isocyanate group of this intermediate was quantified, the theoretical value was 1.34%, whereas the measured value was 1.25%.
Met.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

(Modification of resin) To 100 parts of a solution of vinyl chloride / vinyl acetate / vinyl alcohol copolymer resin (Sekisui Chemical Co., Ltd. S-REC A) in methyl ethyl ketone (solid content 30%), add 3 parts of the above-mentioned intermediate 8
The reaction was carried out at 0 ° C. for 3 hours to obtain a modified resin in which the intermediate and the vinyl resin were bonded. In the modified resin thus obtained, no isocyanate group was found in the infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Example 4 (Preparation of Intermediate) 35 parts of 2,6-tolylene diisocyanate and 110 parts of ethyl acetate were well stirred at 60 ° C., and a terminal mercaptopolydimethylsiloxane (molecular weight 1,
580) 316 parts are gradually dropped to react.

(K, m, and n are values at which the molecular weight is 1,580) After completion of the reaction, 340 parts of a transparent liquid intermediate was obtained by evaporating ethyl acetate.

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate groups of 2,270 / cm remains, and
An absorption band due to the -Si-O-C group was shown at 090 / cm.

Also, when the free isocyanate group of this intermediate was quantified, the theoretical value was 2.39%, whereas the measured value was 2.12%.
Met.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

(K, m, n are the values that make the molecular weight 1,580) (Modification of Resin) To 100 parts of a solution of polyvinyl butyral resin (S-REC B, manufactured by Sekisui Chemical Co., Ltd.) in methyl ethyl ketone (solid content: 30%), 3 parts of the above intermediate is added and reacted at 80 ° C. for 3 hours,
A modified resin in which the intermediate and the vinyl resin were bonded was obtained.

In the obtained modified resin, no isocyanate group was found in the infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Example 5 (Production of intermediate) 52 parts of hexamethylene diisocyanate and 160 of ethyl acetate
450 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight 2,250) having the following structure is gradually added dropwise thereto while stirring well at 60 ° C. for reaction.

(N is the value at which the molecular weight is 2,250) According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group of 2,270 / cm remains, and 1,
An absorption band due to the -Si-O-C group was shown at 090 / cm.

Also, when the free isocyanate group of this intermediate was quantified, the theoretical value was 1.67%, while the measured value was 1.52%.
Met.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

(N is a value at which the molecular weight becomes 2,250) (Modification of resin) While well stirring acrylic polyol (Hitaloid 3001, manufactured by Hitachi Chemical Co., Ltd., solid content 50%), 5 parts of the above-mentioned intermediate and 5 parts of vinyl acetate were mixed. In addition, the reaction was carried out for 4 hours to obtain a modified resin in which the intermediate and the resin were bonded.

In the obtained modified resin, no isocyanate group was found in the infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Comparative Reference Example 1 Polyurethane resin solution before modification in Example 1.

Comparative Reference Example 2 100 parts of a polysiloxane resin (KS-841 manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part of a catalyst (PL-7) attached thereto were mixed with toluene 1,00.
It was dissolved in 0 part to give a polysiloxane resin coating solution.

Evaluation Examples 1 to 5 and Evaluation Comparative Examples 1 and 2 100% modulus 60 Kg /
On one side of polyvinyl chloride film with a thickness of 50 μm in cm ² ,
Apply evenly to a solid content of 0.6 g / m ² and apply
A sample having a release agent layer was prepared by heating and drying at 30 ° C. for 30 seconds. When the temperature was 100 ° C. or higher, the polyvinyl chloride film could not maintain its shape as a softened film.

Acrylic adhesive tape (made by Sekisui Chemical Co., Ltd.) with a width of 20 mm was pressure-bonded onto the coated substrate prepared in this way using a rubber roller with a weight of 2 kg, and it was used at room temperature (20 ° C, humidity 52%) for 1 day and at high temperature (40 ° C,
The peel strength, the residual adhesive strength, the residual adhesive strength retention rate, the peeling property of the peelable coating layer, and the writability with a magic ink after standing for 3 days at a humidity of 90% or more) were measured, and the results are shown in Table 1 below. It was

Evaluation Example 1 100 parts resin solution of Example 1 Coronate L (addition product of trimethylolpropane and TDI) 2 parts Methyl ethyl ketone (MEK) 250 parts Evaluation Example 2 Resin solution of Example 2 100 parts Coronate L 2 parts Fluororesin powder ( Daikin Industries' Lubron L-2) 5
Part MEK 250 parts Evaluation Example 3 100 parts resin solution of Example 3 Coronate L 2 parts MEK 250 parts Evaluation Example 4 Resin solution of Example 4 100 parts Coronate L 2 parts Silicone resin powder (Toshiba Silicone Tospearl 12
0) 5 parts MEK 250 parts Evaluation Example 5 100 parts resin solution of Example 5 Coronate L 2 parts Silicone resin powder (Toshiba Silicone Tospearl 12
0) 5 parts MEK 250 parts Evaluation Comparative Example 1 100 parts resin solution of Comparative Reference Example 1 Silicone oil (SH200 manufactured by Toray Silicone) MEK 250 parts Evaluation Comparative Example 2 100 parts of Resin Solution of Comparative Reference Example 2 Obeyed.

Peel strength: Stick a 20 mm wide adhesive tape on the peelable coating layer, and at 40 ℃
After storing for 24 hours under a load of 20 g / cm ^{2, the} force (g) required for peeling by pulling at an angle of 180 ° at a speed of 300 mm / min was measured (20 ° C).

Residual adhesive strength: The adhesive tape after measuring the peeling property was attached to a stainless steel plate # 280, and it was reciprocated once on a 2 kg tape roller, and after 30 minutes, 3
The force (g) required for peeling by pulling at an angle of 180 ° at a speed of 00 mm / min was measured (20 ° C).

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

Detachability: After the gauze is reciprocated once with a load of 50 g / cm ^{2 on} the releasable coating layer, the releasability test of the releasable coating layer is performed on the sample.

Writability with magic ink: Write on the peelable coating layer with oil-based magic ink on the market,
The presence or absence of ink repellency during writing was examined.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masashi Kashiwamura 4-18-13 Ukima, Kita-ku, Tokyo (72) Inventor Tomoko Goto 4--4-33 Nishi-Aoki, Kawaguchi City, Saitama Prefecture (72) Inventor Katsumi Kuriyama Saitama 1135-1, Shimonoma Kuri, Koshigaya, Japan (56) Reference JP-A-49-7346 (JP, A)

Claims (3)

[Claims] 1. A reaction product of a polysiloxane compound having a reactive group and an organic polyisocyanate, which has a reaction product having at least one free isocyanate group and a group capable of reacting with the isocyanate group. A method for producing a peelable resin, which comprises reacting with a resin. 2. The releasability according to claim 1, wherein the reactive group of the polysiloxane is at least one group selected from an amino group, an epoxy group, a hydroxyl group, a mercapto group and a carboxyl group. Resin manufacturing method. 3. A resin having a group capable of reacting with an isocyanate group is a polyurethane resin, polyurea resin, acrylic resin or vinyl resin.
The method for producing a releasable resin according to item.